CN1811490A - 一类有机－无机杂化的二阶非线性光学薄膜材料 - Google Patents

一类有机－无机杂化的二阶非线性光学薄膜材料 Download PDF

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CN1811490A
CN1811490A CN 200510002445 CN200510002445A CN1811490A CN 1811490 A CN1811490 A CN 1811490A CN 200510002445 CN200510002445 CN 200510002445 CN 200510002445 A CN200510002445 A CN 200510002445A CN 1811490 A CN1811490 A CN 1811490A
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organic
film
film material
thin film
linear optical
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王科志
高丽华
胡晓娟
王丽颖
冯春华
王鸿飞
郑德圣
郭源
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Beijing Normal University
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Beijing Normal University
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Abstract

本发明通过把玻璃或石英基片交替插入含有合适结构的二阶非线性光学活性的有机阳离子和合适结构的无机阴离子的水溶液中，可制得均匀生长的静电自组装多层膜。该膜制备方法简单、快速、造价低和稳定性好，且膜的二次谐波发生强度的平方根随膜层数的增加而线性增加。

Description

一类有机-无机杂化的二阶非线性光学薄膜材料
技术领域
本发明涉及二阶非线性光学薄膜材料技术领域。
背景技术
二阶非线性光学薄膜材料在光电子器件的众多领域有广阔的应用前景。分子在薄膜中要表现出大的宏观二阶非线性光学响应，必须创造非中心对称的分子环境。但象半菁这类具有大的二阶分子超极化率的分子，很容易以中心对称环境成膜或结晶，导致很弱或接近消失的宏观的二阶非线性光学响应。通过Langmuir-Blodgett(LB)技术[1]，可使二阶非线性有机发色团非中心对称叠加，但LB技术需要特殊昂贵的仪器和精细的操作，而且LB膜的稳定性差限制了它的应用。通过共价键的逐层组装[2]，也可创造非中心对称结构的自组装膜，但很难均匀增长到足够的厚度。也有报道用电晕极化技术通过使极性分子在高电场下定向排列，来改进薄膜的非线性光学性质[3]。本专利发明的有机-无机杂化的静电自组装[4]薄膜，其薄膜的二阶非线性信号强度的平方根随薄膜层数的增加线性增加。薄膜制备方法简单易行、快速、成本低。
发明内容
通过阴阳离子的静电吸引，用括号中任何一种无机杂多酸或盐(磷钼酸H3PMo12O40)4·xH2O、钨硅酸H4SiW12O40·xH2O、磷钨酸H3PW12O40·xH2O、纳米环形钼氧簇Na3[Mo154O462H14(H2O)48(HO2C-(NH3 +)HC-CH2-S-S-CH2-CH(NH3 +)-COO2)11]·xH2O)和用图1中任何一种具有电子给体-共轭π体系-电子受体结构的二阶非线性光学活性的有机阳离子制备均匀生长的多层膜，该膜二次谐波发生强度的平方根与膜的层数成正比(见图2)。
具体实施方式
本发明采用的技术方案是：一系列具有电子给体-共轭π体系-电子受体结构的二阶非线性光学活性的有机阳离子的分子结构如图1所示，通过文献[5]的方法合成。传统的无机杂多酸或盐购于试剂公司，而组成为Na3[Mo154O462H14(H2O)48(HO2C-(NH3 +)HC-CH2-S-S-CH2-CH(NH3 +)-COO2)11]·xH2O(x≈250)纳米环形钼氧簇按文献[6]方法合成。静电自组装多层膜的制备方法是：(1)将按文献[7]方法表面氨基化的玻璃或石英基片浸入pH＝3.00的水溶液中10分钟，然后取出N2吹干。(2)将(1)步得到的基片浸入pH＝3.0的0.1mmol/L的无机杂多酸或盐溶液中40分钟后取出，用pH＝3的水溶液反复冲洗表面后，N2吹干。(3)将(2)步得到的基片浸入pH＝3.0的一种有机阳离子(见图1)水溶液中40分钟后取出，用pH＝3的水溶液反复冲洗表面后，N2吹干。重复上述(2)和(3)步骤得到静电自组装多层膜。紫外可见光谱监测薄膜在可见区的最大吸收蜂强度随膜层数的增加线性增长，表明薄膜均匀沉积。采用反射式，用800nm的激光为基频光，测含有不同层数的有机阳离子的薄膜的二次谐波(400nm)发生强度。结果表明，薄膜二次谐波发生强度的平方根与膜的厚度成正比(图2)。
参考文献：
[1](a)Ashwell，G.J.；Walker，T.W.；Leeson，P.；Grummt，U.-W.；Lehmann，F.，Langmuir，1998，14，1525.
(b)Aktsipetrov，O.A.；Akhmediev，N.N.；Mishina，E.D.；Novak，V.R.，JETP Lett.，1983，37，207.(c)Girling，I.R.；Cade，N.A.；Kolinsky，P.V.；Jones，R.J.；Peterson，I.R.；Ahmad，M.M.；Neal，D.B.；Petty，M.C.；.Roberts，G.G.，Feast.W.J.，J.Opt.Soc.Am.，B，1987，4，950.
[2](a)Li，D.，Ratner，M.A.；Marks，T.J.；Zhang，C.H.；Yang，J.；Wong，G.K.，J.Am.Chem.Soc.，1990，112，7389.(b)Katz，H.E.；Scheller，G；Putvinski，T.M.；Schilling，M.L.；Wilson，W.L.；Chidsey，C.E.D.，Science，1991，254，1485.(c)Yitzchaik，S.J.；Roscoe，S.B.；Kakkar，A.K.；Allan，D.S.；Marks，T.J.；Xu，Z.；Zhang，T.；Lin，W.；Wong，G.K.，J.Phys.Chem.，1993，97，6958.(d)Lin，W.；Yitzchaik，S.；Lin，W.；Malik，A.；.Durbin，M.K.；Richter，A.G.；Wong，G.K.；Dutta，P.；Marks，T.J.，Angew.Chem.Int.Ed.Engl.，1995，34，1497.
[3](a)Singer，K.D.；Sohn，J.E.；Lalama，S.J.，Appl.Phys.Lett.，1986，49，248.(b)Jungbauer，D.；Reck，B.；Twieg，R.；Yoon，D.Y.；Wilson，C.G.；Swalen，J.D.，Appl.Phys.Lett.，1990，56，2610.(c)Wu，J.W.；Valley，J.F.；Ermer S.；Binkley，E.S.；Kenney，J.T.；Lipscomb，G.F.；Lytel，R.，Appl.Phys.Lett.，1991，58，225.
[4]Decher，G，Science，1997，277，1232.
[5]Wang，K.Z.，；Huang，C.H.；Xu，G.X.；Xu，Y.；Liu，Y.Q.；Zhu，D.B.；Zhao，X.S.；Xie，X.M.；Wu，N.Z.，Chem.Mater.，1994，6，1986.
[6]Müller，A.；Das，S.K.；Kuhlmann，C.；Bgge，H.；Schmidtmann，M.；Diemann，E.；Krickemeyer，E.；Hormes，J.；Hartwig M.H.；Schindler，M.，Chem.Commun.，2001，655.
[7]张玉琦，高丽华，段智明，王科志，王业亮，高鸿钧，化学学报，2004，62，738.
图1.本发明涉及的成膜有机阳离子的分子结构。
图2.薄膜的二次谐波发生强度的平方根与膜层数的关系。

Claims (4)

  1. 主权项：
  2. 1.通过用说明书附图1中所示的任何一种有机双偶极阳离子和括号中任何一种无机杂多酸或盐(磷钼酸H3PMo12O40)4·xH2O、钨硅酸H4SiW12O40·xH2O、磷钨酸H3PW12O40·xH2O、纳米环形钼氧簇Na3[Mo154O462H14(H2O)48(HO2C-(NH3 +)HC-CH2-S-S-CH2-CH(NH3 +)-COO2)11]·xH2O)制备的静电自组装膜。
  3. 2.上述薄膜的二价非线性光学(二次谐波发生)性质。
  4. 3.与上述薄膜的二价非线性光学(二次谐波发生)性质有关的薄膜器件。
CN 200510002445 2005-01-24 2005-01-24 一类有机－无机杂化的二阶非线性光学薄膜材料 Pending CN1811490A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984152A (zh) * 2010-11-22 2011-03-09 中国科学院新疆理化技术研究所 化合物一水合二苹果酸硼铵非线性光学晶体及其生长方法和用途
CN108074746A (zh) * 2016-11-15 2018-05-25 北京工商大学 具有增强光电转换性能的锌钨系列杂多配合物/半菁衍生物有序薄膜

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984152A (zh) * 2010-11-22 2011-03-09 中国科学院新疆理化技术研究所 化合物一水合二苹果酸硼铵非线性光学晶体及其生长方法和用途
CN108074746A (zh) * 2016-11-15 2018-05-25 北京工商大学 具有增强光电转换性能的锌钨系列杂多配合物/半菁衍生物有序薄膜
CN108074746B (zh) * 2016-11-15 2019-08-06 北京工商大学 具有增强光电转换性能的锌钨系列杂多配合物/半菁衍生物有序薄膜

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