【作者】 张晓光；

【导师】 杨槐；

【作者基本信息】 北京科技大学 ， 材料物理与化学， 2015， 博士

【摘要】 本论文以功能材料在光电防护领域应用为背景,探索新型光电功能材料的技术原理和实现方法。一方面以聚苯胺及其衍生物、手征性向列相液晶、稀土离子共掺杂氟氧化物玻璃为基础,研究了光谱特性可控的膜层材料。另一方面以富勒烯C60、碳纳米管、石墨烯等共轭体系材料为基础,研究了基于非线性光学原理的激光限幅技术。本论文的主要工作和结论如下：(1)通过电化学聚合、电化学掺杂聚合方法,制备并研究了聚苯胺及其衍生物薄膜电致变色性能。实验表明,制备的二苯胺磺酸钠掺杂聚合的聚苯胺薄膜分布均匀,整体附着力、响应速度快,具有较佳的电致变色性能。(2)合成了六种手性1,2-丙二醇衍生物,加入向列相液晶后,可诱导形成了具有热致手性翻转性质的N*相液晶。通过调整具有热致手性翻转特性的手性衍生物和左旋、右旋手性化合物的组成比例,可制备螺距随温度变化可控的N*相液晶。(3)提出了选用氟化物基质和共掺杂Er3+/Nd3+,调整能级之间竞争及辐射和无辐射跃迁的竞争关系,氟氧化物玻璃和氟氧化物玻璃陶瓷的荧光谱验证了稀土离子上转换及中红外发光性质,提高了Er3+掺杂的中红外发光性能。(4)采用原位聚合和乳液聚合的方法制备了聚苯胺-碳纳米管、聚苯乙烯-碳纳米管、聚苯乙烯-C60和聚噻吩-C60复合物。1064nm,40ps脉冲Z-扫描实验表明：四种复合物样品有较强的非线性吸收和光限幅性能。富勒烯C60基复合物光限幅机理是单重激发态非线性反饱和吸收,碳纳米管基复合物的光限幅机理是非线性吸收并诱导散射。共轭体系间相互作用对增强非线性光学性质及光限幅性能具有重要意义。石墨烯及单壁碳纳米管样品制备悬浮液,进行532nm、1064nm,10ns脉宽激光限幅实验,结果表明：样品悬浮液对ns脉冲激光都有宽带限幅性能。利用限幅阈值高低不同的SWNTs-NMP和G-CB分别作为前、后级限幅器制作串联型光限幅器,实现了超低阈值和较高损伤阈值的光限幅性能。石墨烯和单壁碳纳米管悬浮液的光限幅是吸收诱导散射的一种机制。更多还原

【Abstract】 This paper investigates the technical principles and practicability of novel photoelectric functional materials, and their potential application in electro-optics defense. The controllable spectral properties of materials were studied using PANI derivatives with electrochromics, N*-LC with controllable pitch variation and Er3+/Nd3+co-doped oxyfluoride glasses with Mid-infrared. And the nonlinear optical limiting technology of C60、CNTs、Graphene was also studied.Herein, we report our work progress as follows:(1) PANI and its derivatives films were synthesized by using electrochemical polymerization and electrochemical doping techniques to test the film’s electrochromism. The results showed that diphenylamine sulfonate-doped PANI film exhibits good homogeneity, strong affinity, fast response, and excellent electrochromic performance.(2)6Chiral1,2-propanediol derivatives were prepared, which formed chiral nematic crystals (N*-LC) once doped into a nematic liquid crystal. The N*-LCs with controllable pitch variation were obtained by changing the percentage and enantiomeric excess of the chiral dopants.(3) To modify the competition between different energy states and radioactive/non-radioactive transitions, the fluoride with low phonon energy and Er3+/Nd3+co-doped oxyfluoride were proposed, Er3+/Nd3+co-doped oxyfluoride glasses and Er3+doped oxyfluoride Ceramic glass were prepared. The upconversion and Mid-infrared fluorescence properties of Er3+/Nd3+co-doped oxyfluoride glasses were verified.(4) PANI-MWNTs, PS-MWNTs, PS-C60, PTh-C60compounds were synthesized by the in-situ and emulsion polymerization process, which all showed strong nonlinear absorption and optical limiting with laser pulses of40ps using Z-scan technique at1064nm. The optical limiting mechanism of C6o compounds is the single excited-states reverse saturable absorption. Two main mechanisms of the MWNTs compounds are the nonlinear absorption and induced scattering. The interactions between the conjugated polymers are thought to be significant to improve the nonlinear and optical limiting properties. The optical limiting properties of suspensions of graphene and SWNTs were measured. The results showed a broadband optical limiting effect for nanosecond laser pulses at532nm and1064nm. The tandem limiter based on SWNTs-NMP and G-CB was designed, which exhibits a broadband limiting property for low and high damage threshold. Besides, the optical limiting mechanisms of fullerene and SWNT are also absorption and induced scattering.更多还原