JPH01118823A - Organic nonlinear optical element - Google Patents
Organic nonlinear optical elementInfo
- Publication number
- JPH01118823A JPH01118823A JP62275768A JP27576887A JPH01118823A JP H01118823 A JPH01118823 A JP H01118823A JP 62275768 A JP62275768 A JP 62275768A JP 27576887 A JP27576887 A JP 27576887A JP H01118823 A JPH01118823 A JP H01118823A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- fluorenone
- medium
- nonlinear
- thermal stability
- 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 61
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 abstract description 8
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- -1 2- Nitro-9-fluorenone-4-fluorenecarboxylate-6-amino-9-fluorenone Chemical compound 0.000 description 5
- AJEAHBZZHSLIQP-UHFFFAOYSA-N 2-nitrofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 AJEAHBZZHSLIQP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004219 molecular orbital method Methods 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WWFXOQURMTWRBT-UHFFFAOYSA-N 1,1,4,4,4-pentafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CCC(F)(F)F WWFXOQURMTWRBT-UHFFFAOYSA-N 0.000 description 1
- VDFKURANQKCOAI-UHFFFAOYSA-N 1-nitrofluoren-9-one Chemical compound C12=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] VDFKURANQKCOAI-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 238000004972 CNDO calculation Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910003327 LiNbO3 Inorganic materials 0.000 description 1
- HCVBBVTZZJFVLA-NSHDSACASA-N [(2s)-1-(4-nitrophenyl)pyrrolidin-2-yl]methanol Chemical compound OC[C@@H]1CCCN1C1=CC=C([N+]([O-])=O)C=C1 HCVBBVTZZJFVLA-NSHDSACASA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
- G02F1/3613—Organic materials containing Sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
- C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
- C07C49/675—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system having three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D311/86—Oxygen atoms, e.g. xanthones
-
- 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
- G02F1/3611—Organic materials containing Nitrogen
-
- 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
- G02F1/3611—Organic materials containing Nitrogen
- G02F1/3612—Heterocycles having N as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、非線形光学効果を利用した光変調素子に係り
、特に、第二、第三高調波発生、光混合光パラメトリツ
ク発振、光スィッチ、光双安定素子等の非線形光学素子
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an optical modulation device that utilizes nonlinear optical effects, and in particular, to second and third harmonic generation, optical mixing optical parametric oscillation, and optical switching. , relates to nonlinear optical elements such as optical bistable elements.
非線形光学素子は、電磁場による二次、三次の非線形分
極を利用し、高調波発生、光混合、光パラメトリツク発
振、光スィッチ等の素子として使われる。又、将来実現
すると予想される光コンピュータの基本素子となり得る
光双安定素子としても注目を浴びている。Nonlinear optical elements utilize second- and third-order nonlinear polarization caused by electromagnetic fields and are used for harmonic generation, optical mixing, optical parametric oscillation, optical switches, etc. Furthermore, it is attracting attention as an optical bistable element that can become a basic element of optical computers that are expected to be realized in the future.
従来、非線形光学用素子材料としては、ニオブ酸リチウ
ム（ＬｉＮｂＯ３）、リン酸二水素カリウム（ＫＤＰ）
、砒化ガリウム（ＧａＡｓ）などの無機材料及び半導体
材料が主に検討されてきた。Conventionally, lithium niobate (LiNbO3) and potassium dihydrogen phosphate (KDP) have been used as nonlinear optical element materials.
, inorganic materials such as gallium arsenide (GaAs), and semiconductor materials have mainly been considered.
近年、それらの材料に比べ、非線形光学性能に優れ（士
ないし百倍）、又、光双安定を利用した光ＩＣ等で重要
となる光応答速度が非常に速い有機系の非線形光学材料
があいついで発見され、基礎から応用にわたった広範囲
研究が盛んになってきた。それらの有機材料には、尿素
、２−メチルー４−ニトロアニリン（ＭＮＡ）（特開昭
５５−５００９６０号公報）、Ｎ−（４−二トロフェニ
ル）−Ｌ−プロリノール（ＮＰＰ）（特開昭５９−２１
１６６５号公報）などがあげられる。In recent years, an increasing number of organic nonlinear optical materials have been developed that have superior nonlinear optical performance (up to 100 times better) than those materials, and have extremely fast optical response speeds, which are important for optical ICs that utilize optical bistable technology. Since its discovery, wide-ranging research ranging from basics to applications has become active. These organic materials include urea, 2-methyl-4-nitroaniline (MNA) (JP-A-55-500960), N-(4-nitrophenyl)-L-prolinol (NPP) (JP-A-55-500960), Showa 59-21
Publication No. 1665).
先にあげた従来の非線形光学材料は、非線形光学定数が
大きく基本的性能の面で優れている。しかし、その反面
、大きな質的に優れた単結晶を作成することが困難であ
る点、結晶の安定性、耐性等が悪い点、透明性が無い等
の問題点があった。The conventional nonlinear optical materials listed above have large nonlinear optical constants and are excellent in basic performance. However, on the other hand, there are problems such as difficulty in producing large and qualitatively superior single crystals, poor crystal stability and durability, and lack of transparency.
これらの問題点のうち、熱的安定性は、実用上の観点か
らは、特に改善されなければならない点である。一般に
、有機非線形光学材料の優れたものは、無機のそれに比
し、光損傷しきい値（瞬間的な光射性）は、かなり大き
い。しかし、有機材料は、長時間光にさらされた場合の
耐性は、それ程大きいとは言えない。なぜなら、光エネ
ルギが熱に変換され、一般に有機材料は熱的安定性が悪
いためである。従って、有機非線形光学材料の実用上の
安定性、耐性を考える場合、熱的安定性は非常に重要な
ポイントとなる。この観点から、有機非線形光学材料の
融点は高い程（２００℃以上が）望ましい。残念ながら
、大きな非線形性能をもつ有機材料で、かつ、この点を
満足した非線形光学材料は未だ見出されていない。特に
、高出力の光処理を考える場合、この点は非常に重要な
改善すべき点となる。Among these problems, thermal stability is one that must be particularly improved from a practical standpoint. In general, superior organic nonlinear optical materials have a significantly higher optical damage threshold (instantaneous light emitting property) than inorganic materials. However, organic materials cannot be said to be very resistant to long-term exposure to light. This is because light energy is converted into heat, and organic materials generally have poor thermal stability. Therefore, when considering the practical stability and durability of organic nonlinear optical materials, thermal stability is a very important point. From this point of view, the higher the melting point of the organic nonlinear optical material (200° C. or higher), the more desirable it is. Unfortunately, a nonlinear optical material that has a large nonlinear performance and satisfies this requirement has not yet been found. Especially when considering high-power optical processing, this point is a very important point to be improved.
ここで与えられた課題は、大きな非線形光学性能をもち
、かつ、熱的に安定な非線形光学素子を開発することで
ある。この目的は、非線形媒質として、大きな非線形光
学定数をもち、かつ、熱的に安定な、すなわち、融点が
高く高温まで熱破壊を起こさない有機非線形光学材料を
用いることにより達成される。この様な有機非線形光学
材料とは、フルオレノン及びその誘導体、フルオレノン
及びその誘導体を側鎖及び主鎖に含んだ高分子、及び、
組成物としてフルオレノン及びその誘導体を含む高分子
である。より具体的に、フルオレノン誘導体とは、２−
ニトロ−９−フルオレノン−４−フルオレンカルボキシ
レート
−６−アミツー−９−フルオレノン
リ
等である。The challenge here is to develop a thermally stable nonlinear optical element with high nonlinear optical performance. This objective is achieved by using as a nonlinear medium an organic nonlinear optical material that has a large nonlinear optical constant and is thermally stable, that is, has a high melting point and does not cause thermal breakdown even at high temperatures. Such organic nonlinear optical materials include fluorenone and its derivatives, polymers containing fluorenone and its derivatives in the side chain and main chain, and
It is a polymer containing fluorenone and its derivatives as a composition. More specifically, fluorenone derivatives are 2-
Nitro-9-fluorenone-4-fluorenecarboxylate-6-amino-9-fluorenone and the like.
フルオレノン及びその誘導体を主鎖及び側鎖の化学構造
中に含む高分子とは、上記にあげた様なフルオレノン及
びその誘導体が、高分子の七ツマ−１例えば、アクリル
酸、メタクリル酸、スチレンなどと、エステル結合、ア
ミド結合、又は、炭素炭素結合によって結合し、重合し
たものである。Polymers containing fluorenone and its derivatives in the chemical structure of the main chain and side chains are those in which the above-mentioned fluorenone and its derivatives are polymers such as acrylic acid, methacrylic acid, styrene, etc. and are bonded together through ester bonds, amide bonds, or carbon-carbon bonds and polymerized.
フルオレノン、及び、その誘導体を組成物として含む高
分子とは、上記の様なフルオレノン及びその誘導体を、
アクリル酸、メチルアクリレート、エチルアクリレート
、ブチルアクリレート、イソブチルアクリレート、メタ
クリル酸、メチルメタクリレート、エチルメタクリレー
ト、ｍ−ブチルメタクリレート、イソブチルメタクリレ
ート、トリエチルプロパンメタクリレート、ｍ−へキシ
ルメタクリレート、シクロへキシルメタクリレート、フ
ェニルメタクリレート、ベンジルメタクリレート、エチ
レングリコールジメタクリレート、グリシジルメタクリ
レート、ペンタフルオロブチルメタクリルート、スチレ
ン、クロロスチレン、２゜５−ジクロロスチレン、メト
キシスチレン等に混合し重合させたものである。A polymer containing fluorenone and its derivatives as a composition refers to the above-mentioned fluorenone and its derivatives,
Acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, m-butyl methacrylate, isobutyl methacrylate, triethylpropane methacrylate, m-hexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, It is mixed with benzyl methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, pentafluorobutyl methacrylate, styrene, chlorostyrene, 2°5-dichlorostyrene, methoxystyrene, etc. and polymerized.
又、必要に応じて、重合後ポーリング処理を行うことに
より、フルオレン及びその誘導体を配向させることがで
き、高分子非線形光学材料の非線形性能を向上させるこ
とができる。Further, if necessary, by performing a poling treatment after polymerization, fluorene and its derivatives can be oriented, and the nonlinear performance of the polymeric nonlinear optical material can be improved.
一般に、非線形光学定数（特に二次）の大きい有機材料
は、まず、必要条件として、その構成分子が大きな非線
形光学定数を持つ必要がある。次にそれらの分子が、そ
の非線形状をマクロな物性として有効に反映する様に凝
集する（結晶化する）ことが必要である。Generally, organic materials with large nonlinear optical constants (especially quadratic) require that their constituent molecules have large nonlinear optical constants. Next, it is necessary for these molecules to aggregate (crystallize) so that their nonlinear shape is effectively reflected as macroscopic physical properties.
まず、分子として大きな非線形光学定数を示すためには
、その骨格にπ電子共役系が存在し、さらに置換基とし
て、電子供与基及び電子吸引性基をもつことが重要であ
る。しかし、これは一般論であり、π共役系をもつ骨格
として具体的にどの様な骨格が適当であるか、又、置換
基として何が適当かを選定するのは非常に難しい。そこ
で、我我は、分子構造より、分子軌道法を用いて分子の
非線形光学定数を予測し、ｄｃ−８ＨＧ法による実測を
もあわせて、分子設計を行った。First, in order for the molecule to exhibit a large nonlinear optical constant, it is important that the molecule has a π-electron conjugated system in its skeleton, and that it also has an electron-donating group and an electron-withdrawing group as substituents. However, this is a general theory, and it is very difficult to specifically select what kind of skeleton is suitable as a skeleton having a π-conjugated system and what is suitable as a substituent. Therefore, we designed the molecule by predicting the nonlinear optical constants of the molecule based on the molecular structure using the molecular orbital method, and also using actual measurements using the dc-8HG method.
又、第二の凝集構造に関しても、エネルギ計等の手法を
用い解析予測しつつ、上記の目的に適した分子構造の選
定を行った。Regarding the second agglomerated structure, a molecular structure suitable for the above purpose was selected while analyzing and predicting it using methods such as an energy meter.
又、有機非線形光学材料が熱的に安定、すなわち、高融
点を示すためには、結晶形成時の凝集エネルギが大きく
、かつ、融解時のエネメロピ増加が小さいような分子構
造を選定すればよい。In addition, in order for the organic nonlinear optical material to be thermally stable, that is, to exhibit a high melting point, a molecular structure that has a large cohesive energy during crystal formation and a small increase in energy efficiency during melting may be selected.
フルオレノン及びその誘導体では、上述の諸点が有効に
作用しあい、極めて大きな非線形性を示し、かつ、高温
まで熱的に安定である。Fluorenone and its derivatives exhibit extremely large nonlinearity due to the effective interaction of the above points and are thermally stable up to high temperatures.
本発明の内容を以下実施例に基づいて詳細に説明する。 The content of the present invention will be explained in detail below based on examples.
〈実施例１〉
フルオレノン及びその誘導体の分子構造を分子力学的手
法により最適化し、半経験的分子軌道法ＣＮＤＯ／Ｓ３
−ＣＩを用いて、最大励起波長λｍａｘ 、及び、分子
の二次非線形分板率βの値を算出した。<Example 1> The molecular structure of fluorenone and its derivatives was optimized by molecular mechanical techniques, and semi-empirical molecular orbital method CNDO/S3
-CI was used to calculate the maximum excitation wavelength λmax and the second-order nonlinear splitting ratio β of the molecule.
次に、各試料のβの値をｄａ−８ＨＧ法により実測した
。具体的には、試料をエタノールに溶解させ、５ｋＶ、
２ＩＩｓのパルス電圧を印加し、それに同期してピーク
パワー１００ＭＷ、 １０ＩｌｌｓのパルスＹＡＧレー
ザ光（波長１．０６ μｍ）を試料に照射し、波長５
３０ｍｍの波長変換光を光電子増倍管により測定した。Next, the value of β of each sample was actually measured using the da-8HG method. Specifically, the sample was dissolved in ethanol, 5kV,
A pulse voltage of 2IIs was applied, and in synchronization with this, the sample was irradiated with pulsed YAG laser light (wavelength 1.06 μm) with a peak power of 100MW and 10Ills.
The wavelength-converted light of 30 mm was measured using a photomultiplier tube.
同様の方法により測定したニトロベンゼン純液体の出力
光をリファレンスとしてβの値を見積った。β及びλｍ
ａｘの計算値及び、βの実測値を表１に示した。なお、
比較のためＭＮＡの値も同時に表１に示した。The value of β was estimated using the output light of a pure nitrobenzene liquid measured by a similar method as a reference. β and λm
Table 1 shows the calculated value of ax and the measured value of β. In addition,
For comparison, the MNA values are also shown in Table 1.
次に粉末法により、結晶の非線形光学定数を測定した。Next, the nonlinear optical constants of the crystal were measured using the powder method.
まず、試料を乳針ですりつぶし、粒径を１００μｍ程度
にそろえた後、上述のＱ−スナツチＹＡＧレーザ光を照
射し、波長５３０ｍ５の波長変換光を集光レンズで集め
、各種フィルタで５３Ｏｎ＋＋ａ以外の光をカットし強
度洞室を行った。First, the sample is ground with a milk needle to make the particle size about 100 μm, and then the above-mentioned Q-Snatchi YAG laser beam is irradiated, the wavelength-converted light with a wavelength of 530 m5 is collected with a condensing lens, and various filters are used to I cut the light and performed an intensity sinus chamber.
表２に測定結果を対尿素比として示した。Table 2 shows the measurement results as a ratio to urea.
次に熱的安定性を見るため、ＴＧ（熱重量測定）ＤＳＣ
測定を行った。融点に関しては、表２に、又、ＴＧ−Ｄ
ＳＣ測定に関しては、代表例として、表 ２
２−ニトロ−９−フルオレノンの結果を第２図に示した
。これをみると、２−ニトロ−９−フルオレノンは融点
２２３℃まで熱的に非常に安定であり、熱分解等を起こ
さないことがわかる。Next, to check the thermal stability, TG (thermogravimetry) DSC
Measurements were taken. Regarding the melting point, see Table 2, and TG-D
Regarding the SC measurement, the results for 2-nitro-9-fluorenone in Table 2 are shown in FIG. 2 as a representative example. This shows that 2-nitro-9-fluorenone is very thermally stable up to its melting point of 223°C and does not undergo thermal decomposition.
〈実施例２〉
第二高調波発生を利用した波長変換素子の概略図を第２
図に示した。非線形光学媒体は、フルオレノン及びその
誘導体を用い、基板上に波相エピタキシャル成長法で薄
膜状の単結晶を成長させ、素子を作成した。位相整合が
とれる物質の場合、バルク単結晶をそのまま素子化する
ことが可能である。この場合の単結晶は、６０℃の飽和
エタノール溶液を恒温槽中で毎分０．０３ ℃の割合で
徐冷す乞ことにより得ら゛れる。<Example 2> A schematic diagram of a wavelength conversion element using second harmonic generation is shown in the second example.
Shown in the figure. The nonlinear optical medium used fluorenone and its derivatives, and a thin film-like single crystal was grown on a substrate by a wave phase epitaxial growth method to create an element. In the case of a substance that can achieve phase matching, it is possible to turn a bulk single crystal into a device as it is. In this case, the single crystal is obtained by slowly cooling a saturated ethanol solution at 60° C. in a constant temperature bath at a rate of 0.03° C. per minute.
素子にピークパワーを１００ｋＷ、１００ＰｓのＹＡＧ
レーザ光（波長１．０６ μｍ）を入射させ、波長５３
０ｍａの第二高調波を光電子増倍管により測定した。変
換効率は、尿素と比較して、２−ニトロ−９−フルオレ
ノンの場合、二十倍であった。YAG element with peak power of 100kW and 100Ps
Laser light (wavelength 1.06 μm) is incident, and the wavelength is 53 μm.
The second harmonic at 0 ma was measured using a photomultiplier tube. The conversion efficiency was twenty times higher for 2-nitro-9-fluorenone compared to urea.
〈実施例３〉
組成物として、フルオレン及びその誘導体を含む高分子
の作成例をあげる。２−ニトロ−９−フルオレノンＬｏ
ｇをメチルメタクリレート５０ｇに溶解させ、重合開始
剤としてラウロイルパーオキシドを０．０２重量パーセ
ンサ加えた後、６０℃で四十へ時間重合させた。得られ
た重合生成物をポーリング処理し、分子を配向させた。<Example 3> An example of preparing a polymer containing fluorene and its derivatives will be given as a composition. 2-nitro-9-fluorenone Lo
g was dissolved in 50 g of methyl methacrylate, 0.02 weight percent of lauroyl peroxide was added as a polymerization initiator, and the mixture was polymerized at 60° C. for 40 hours. The obtained polymerization product was subjected to a poling treatment to orient the molecules.
これを用いて素子を作成し、実施例２と同様の操作でＹ
ＡＧレーザ光の第二高調波への変換効率を求めたところ
、尿素の十五倍であった。An element was created using this, and Y
When the conversion efficiency of AG laser light to the second harmonic was determined, it was found to be 15 times that of urea.
本発明の素子は１本非線形光学材料の本質的な特性を利
用したものであるので、実施例であげた第二高調波を利
用した波長変換素子のみならず。Since the element of the present invention utilizes the essential characteristics of a single nonlinear optical material, it is applicable not only to the wavelength conversion element using the second harmonic as mentioned in the embodiment.
広く非線形光学素子として動作させることができる。It can be widely operated as a nonlinear optical element.
本発明によれば、熱的に安定であり、非線形光学性能が
優れた材料を使用した、効率的に動作する非線形光学素
子が得られる。According to the present invention, it is possible to obtain an efficiently operating nonlinear optical element using a material that is thermally stable and has excellent nonlinear optical performance.
第１図は本発明の一実施例の有機非線形光学素子の説明
図、第２図は本発明中の非線形光学媒体の一例である２
−ニトロ−９−フルオレノンのＴＯ−ＤＳＣ曲線である
。
１・・・レーザ光、３・・・薄膜状の有機非線形光学媒
体。FIG. 1 is an explanatory diagram of an organic nonlinear optical element according to an embodiment of the present invention, and FIG. 2 is an example of a nonlinear optical medium according to the present invention.
- TO-DSC curve of nitro-9-fluorenone. 1... Laser light, 3... Thin film organic nonlinear optical medium.
Claims (1)
素子に於いて、 非線形光学媒質が、フルオレノン及びその誘導体よりな
ることを特徴とする有機非線形光学素子。 ２、特許請求の範囲第１項において、 前記非線形光学媒質が、フルオレノン及びその誘導体を
側鎖及び主鎖に含んだ高分子よりなることを特徴とする
有機非線形光学素子。 ３、特許請求の範囲第１項において、 前記非線形光学媒質が、組成物としてフルオレノン及び
その誘導体を含む高分子よりなることを特徴とする有機
非線形光学素子。[Claims] 1. An organic nonlinear optical element that performs optical modulation using a nonlinear optical effect, characterized in that the nonlinear optical medium is made of fluorenone and its derivatives. 2. The organic nonlinear optical element according to claim 1, wherein the nonlinear optical medium is made of a polymer containing fluorenone and its derivatives in the side chain and main chain. 3. The organic nonlinear optical element according to claim 1, wherein the nonlinear optical medium is made of a polymer containing fluorenone and its derivatives as a composition.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62275768A JPH01118823A (en) | 1987-11-02 | 1987-11-02 | Organic nonlinear optical element |
| EP88118238A EP0315140B1 (en) | 1987-11-02 | 1988-11-02 | Non-linear optical device |
| DE3854341T DE3854341T2 (en) | 1987-11-02 | 1988-11-02 | Nonlinear optical substance. |
| US07/711,414 US5176854A (en) | 1987-11-02 | 1991-06-05 | Non-linear optical device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62275768A JPH01118823A (en) | 1987-11-02 | 1987-11-02 | Organic nonlinear optical element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01118823A true JPH01118823A (en) | 1989-05-11 |
Family
ID=17560122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62275768A Pending JPH01118823A (en) | 1987-11-02 | 1987-11-02 | Organic nonlinear optical element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01118823A (en) |
-
1987
- 1987-11-02 JP JP62275768A patent/JPH01118823A/en active Pending
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