适用于全光开关的两种金属DMIT配合物材料的制备与性能研究
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摘要
在信息化时代,人们对信息的需求量急剧增加,传统的通信技术已经很难满足不断增长的通信容量的要求。光通信技术因为其潜在的带宽容量的特点,成为最重要的通信技术之一。但是,在目前的光通信系统的转换过程中存在着严重串话、高功耗等问题,很容易造成“信息瓶颈”现象。为了解决这一问题,全光开关因为其抗电磁性强和速度快等特点,引起了研究者的重视。在全光开关中数据从源节点到目的节点的传输过程都在光域内进行的。全光开关对材料的基本性能的要求是：在工作波段有大的三阶非线性折射率、低的线性和非线性吸收、超快的非线性光学响应以及优异的物理化学稳定性。
本课题组一直致力于寻找适用于全光开关的三阶非线性光学材料。研究发现,过渡金属的1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基(DMIT)类有机配合物材料具有大的平面共轭结构,易发生极化和电荷转移,金属和有机体系之间的电荷转移可以进一步增强材料的三阶非线性光学性质,因而可能具有大的非线性折射率,小的线性和非线性吸收,在全光开关器件的研制中具有潜在的应用价值。本论文在前期工作的基础上,继续探索新型材料,并对影响材料三阶非线性光学性能的多种因素进行了研究和分析。主要内容如下：
第一,根据全光开关对材料的要求,结合DMIT类材料具有平面π电子共轭结构的特点,通过改变金属离子和配合物阳离子,设计合成了几类DMIT有机金属配合物：二(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)合金盐((R4N)Au(DMIT)2其中,R为C2H5、C3H7和C4H9)；二(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)合锰盐((RR'3N)2Mn(DMIT)2 (R为C4H9,C3H5和C6H4-CH3,R'为C4H9,CH3,C6H5)。其中,((C4H9)4N)2Mn(DMIT)2新材料的结构和三阶非线性光学性质被首次报道。
第二,对合成的几类DMIT有机金属配合物,二(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)合M盐(M=Au,Mn),系统研究了它们的基本物理化学性质,包括热分析、红外光谱和线性吸收谱图；并采用激光Z扫描方法研究了金、锰和镍的几类DMIT配合物的三阶非线性光学特性,在1064nm,20ps等脉冲激光照射条件下,得到了这些材料的三阶非线性极化率、非线性折射率和非线性吸收系数等非线性光学参数。
第三,着重对影响材料三阶非线性光学特性的因素进行了研究,得到了一系列重要结果：DMIT类配合物外部阳离子仅会对材料的三阶非线性光学特性的强弱产生影响；决定DMIT类配合物材料的线性和非线性光学特性的主要因素是中心金属离子；发现金和锰的材料在近红外波段满足全光开关对材料品质因子W=n2I/α0λ和T=βλ/n2(且|W|>>1,|T|<<1)的要求。
综上,本论文通过改变DMIT有机金属配合物的外部阳离子和中心金属离子等,设计和探索具有超快响应速度的三阶非线性光学材料,通过材料筛选,获得了几种对全光开关有潜在应用前景的非线性光学材料。
In the information age, since the demand of information for people increase sharply, the traditional communication technology has been difficult to meet the growing capacity requirements of communication. The optical communication technology becomes the most important communication technology for its potential bandwidth capacity. However, optical communication system in the current process of converting has some issues, such as a serious cross talk and high power consumption and so on, which lead to the phenomenon of information bottleneck. In order to solve the problems, all-optical switching (AOS) has been paid dramatic attention because of its strong resistance electromagnetic and fast response. In the AOS, the data transfer process from the source node to destination node in the optical domain transfer process is carried out in the optical domain. To be practically useful for AOS, materials should have a large nonlinear refractive index at the operation wavelength, a low linear and nonlinear absorption and an ultrafast response time, together with good physicochemical properties.
Our group has done in-depth studies on the third-order nonlinear optical (NLO) materials for AOS applications. The research results exhibits that transition metal 1,3-dithiole-2-thioxo-4,5-dithiolato (DMIT) complex, coordination complexes possess largeπ-electron delocalization, charge transfer and high electromigration rate in the systems, so the materials may possess large nonlinear refraction, small linear and nonlinear absorption. They have potential valuable application on AOS devices. Based on the previous work, a continued research work on the exploration some new materials to meet the AOS. Several factors affecting the third-order NLO performance have been also investigated. The main work is as follows:
Firstly, according to the demands of AOS and the characteristics of largeπ-electron delocalization for DMIT materials, through changing metal ions and cations, several kinds of metal-DMIT coordination complexes (R4N)Au(DMIT)2 (R=C2H5, C3H7, C4H9);((RR'3N)2Mn(DMIT)2(R=C4H9,C3H5和C6H4-CH3, R'为C4H9, CH3, C6H5), have been synthesized. Among them, the crystal structure and third-order NLO properties of (C4H9)4N)2Mn(DMIT)2 have been first reported.
Secondly, the basic physicochemical properties, including thermal, infrared (IR) and linear optical absorption, have been studied thoroughly. The third-order NLO characteristics of Au-, Mn- and Ni-DMIT complexes have been investigated by using Z-scan technique. The NLO parameters, such as second hyperpolarizability, nonlinear refraction coefficient and nonlinear absorption coefficient, have been obtained.
Thirdly, the influence factors for the third-order NLO characteristics of materials have been studied and a series of important results have been obtained:the external cations only have very small effects on the third-order NLO characteristics of the DMIT complexes. The main factor for the third-order NLO characteristics is the center metal ion. It is discovered that Au- and Mn-DMIT materials satisfy the requirements of two quality factors for the AOS device (W=n2I0/α0λ, T=βλ/n2 and |W|>>1,|T|<<1).
In summary, this paper designed and explored third-order nonlinear optical materials with fast response time through changing the external cations or the central metal ions of dmit organometallic complexes. We obtained several nonlinear optical materials which have potential applications in all-optical switching through the selection of materials.
本课题组一直致力于寻找适用于全光开关的三阶非线性光学材料。研究发现,过渡金属的1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基(DMIT)类有机配合物材料具有大的平面共轭结构,易发生极化和电荷转移,金属和有机体系之间的电荷转移可以进一步增强材料的三阶非线性光学性质,因而可能具有大的非线性折射率,小的线性和非线性吸收,在全光开关器件的研制中具有潜在的应用价值。本论文在前期工作的基础上,继续探索新型材料,并对影响材料三阶非线性光学性能的多种因素进行了研究和分析。主要内容如下：
第一,根据全光开关对材料的要求,结合DMIT类材料具有平面π电子共轭结构的特点,通过改变金属离子和配合物阳离子,设计合成了几类DMIT有机金属配合物：二(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)合金盐((R4N)Au(DMIT)2其中,R为C2H5、C3H7和C4H9)；二(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)合锰盐((RR'3N)2Mn(DMIT)2 (R为C4H9,C3H5和C6H4-CH3,R'为C4H9,CH3,C6H5)。其中,((C4H9)4N)2Mn(DMIT)2新材料的结构和三阶非线性光学性质被首次报道。
第二,对合成的几类DMIT有机金属配合物,二(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫基)合M盐(M=Au,Mn),系统研究了它们的基本物理化学性质,包括热分析、红外光谱和线性吸收谱图；并采用激光Z扫描方法研究了金、锰和镍的几类DMIT配合物的三阶非线性光学特性,在1064nm,20ps等脉冲激光照射条件下,得到了这些材料的三阶非线性极化率、非线性折射率和非线性吸收系数等非线性光学参数。
第三,着重对影响材料三阶非线性光学特性的因素进行了研究,得到了一系列重要结果：DMIT类配合物外部阳离子仅会对材料的三阶非线性光学特性的强弱产生影响；决定DMIT类配合物材料的线性和非线性光学特性的主要因素是中心金属离子；发现金和锰的材料在近红外波段满足全光开关对材料品质因子W=n2I/α0λ和T=βλ/n2(且|W|>>1,|T|<<1)的要求。
综上,本论文通过改变DMIT有机金属配合物的外部阳离子和中心金属离子等,设计和探索具有超快响应速度的三阶非线性光学材料,通过材料筛选,获得了几种对全光开关有潜在应用前景的非线性光学材料。
In the information age, since the demand of information for people increase sharply, the traditional communication technology has been difficult to meet the growing capacity requirements of communication. The optical communication technology becomes the most important communication technology for its potential bandwidth capacity. However, optical communication system in the current process of converting has some issues, such as a serious cross talk and high power consumption and so on, which lead to the phenomenon of information bottleneck. In order to solve the problems, all-optical switching (AOS) has been paid dramatic attention because of its strong resistance electromagnetic and fast response. In the AOS, the data transfer process from the source node to destination node in the optical domain transfer process is carried out in the optical domain. To be practically useful for AOS, materials should have a large nonlinear refractive index at the operation wavelength, a low linear and nonlinear absorption and an ultrafast response time, together with good physicochemical properties.
Our group has done in-depth studies on the third-order nonlinear optical (NLO) materials for AOS applications. The research results exhibits that transition metal 1,3-dithiole-2-thioxo-4,5-dithiolato (DMIT) complex, coordination complexes possess largeπ-electron delocalization, charge transfer and high electromigration rate in the systems, so the materials may possess large nonlinear refraction, small linear and nonlinear absorption. They have potential valuable application on AOS devices. Based on the previous work, a continued research work on the exploration some new materials to meet the AOS. Several factors affecting the third-order NLO performance have been also investigated. The main work is as follows:
Firstly, according to the demands of AOS and the characteristics of largeπ-electron delocalization for DMIT materials, through changing metal ions and cations, several kinds of metal-DMIT coordination complexes (R4N)Au(DMIT)2 (R=C2H5, C3H7, C4H9);((RR'3N)2Mn(DMIT)2(R=C4H9,C3H5和C6H4-CH3, R'为C4H9, CH3, C6H5), have been synthesized. Among them, the crystal structure and third-order NLO properties of (C4H9)4N)2Mn(DMIT)2 have been first reported.
Secondly, the basic physicochemical properties, including thermal, infrared (IR) and linear optical absorption, have been studied thoroughly. The third-order NLO characteristics of Au-, Mn- and Ni-DMIT complexes have been investigated by using Z-scan technique. The NLO parameters, such as second hyperpolarizability, nonlinear refraction coefficient and nonlinear absorption coefficient, have been obtained.
Thirdly, the influence factors for the third-order NLO characteristics of materials have been studied and a series of important results have been obtained:the external cations only have very small effects on the third-order NLO characteristics of the DMIT complexes. The main factor for the third-order NLO characteristics is the center metal ion. It is discovered that Au- and Mn-DMIT materials satisfy the requirements of two quality factors for the AOS device (W=n2I0/α0λ, T=βλ/n2 and |W|>>1,|T|<<1).
In summary, this paper designed and explored third-order nonlinear optical materials with fast response time through changing the external cations or the central metal ions of dmit organometallic complexes. We obtained several nonlinear optical materials which have potential applications in all-optical switching through the selection of materials.
引文
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