【摘要】：本論文以功能材料在光電防護(hù)領(lǐng)域應(yīng)用為背景,探索新型光電功能材料的技術(shù)原理和實(shí)現(xiàn)方法。一方面以聚苯胺及其衍生物、手征性向列相液晶、稀土離子共摻雜氟氧化物玻璃為基礎(chǔ),研究了光譜特性可控的膜層材料。另一方面以富勒烯C60、碳納米管、石墨烯等共軛體系材料為基礎(chǔ),研究了基于非線性光學(xué)原理的激光限幅技術(shù)。 本論文的主要工作和結(jié)論如下： (1)通過電化學(xué)聚合、電化學(xué)摻雜聚合方法,制備并研究了聚苯胺及其衍生物薄膜電致變色性能。實(shí)驗(yàn)表明,制備的二苯胺磺酸鈉摻雜聚合的聚苯胺薄膜分布均勻,整體附著力、響應(yīng)速度快,具有較佳的電致變色性能。 (2)合成了六種手性1,2-丙二醇衍生物,加入向列相液晶后,可誘導(dǎo)形成了具有熱致手性翻轉(zhuǎn)性質(zhì)的N*相液晶。通過調(diào)整具有熱致手性翻轉(zhuǎn)特性的手性衍生物和左旋、右旋手性化合物的組成比例,可制備螺距隨溫度變化可控的N*相液晶。 (3)提出了選用氟化物基質(zhì)和共摻雜Er3+/Nd3+,調(diào)整能級之間競爭及輻射和無輻射躍遷的競爭關(guān)系,氟氧化物玻璃和氟氧化物玻璃陶瓷的熒光譜驗(yàn)證了稀土離子上轉(zhuǎn)換及中紅外發(fā)光性質(zhì),提高了Er3+摻雜的中紅外發(fā)光性能。 (4)采用原位聚合和乳液聚合的方法制備了聚苯胺-碳納米管、聚苯乙烯-碳納米管、聚苯乙烯-C60和聚噻吩-C60復(fù)合物。1064nm,40ps脈沖Z-掃描實(shí)驗(yàn)表明：四種復(fù)合物樣品有較強(qiáng)的非線性吸收和光限幅性能。富勒烯C60基復(fù)合物光限幅機(jī)理是單重激發(fā)態(tài)非線性反飽和吸收,碳納米管基復(fù)合物的光限幅機(jī)理是非線性吸收并誘導(dǎo)散射。共軛體系間相互作用對增強(qiáng)非線性光學(xué)性質(zhì)及光限幅性能具有重要意義。 石墨烯及單壁碳納米管樣品制備懸浮液,進(jìn)行532nm、1064nm,10ns脈寬激光限幅實(shí)驗(yàn),結(jié)果表明：樣品懸浮液對ns脈沖激光都有寬帶限幅性能。利用限幅閾值高低不同的SWNTs-NMP和G-CB分別作為前、后級限幅器制作串聯(lián)型光限幅器,實(shí)現(xiàn)了超低閾值和較高損傷閾值的光限幅性能。石墨烯和單壁碳納米管懸浮液的光限幅是吸收誘導(dǎo)散射的一種機(jī)制。
[Abstract]:Based on the application of functional materials in the field of optoelectronic protection, this paper explores the technical principles and implementation methods of new optoelectronic functional materials. On the one hand, based on Polyaniline and its derivatives, chiral nematic liquid crystal and rare earth ion co-doped fluorooxide glass, the controllable spectral properties of the film were studied. On the other hand, based on the conjugated materials such as fullerene C60, carbon nanotubes and graphene, the laser limiting technique based on nonlinear optical principle is studied. The main work and conclusions are as follows: (1) Electrochromic properties of Polyaniline and its derivatives thin films were prepared and studied by electrochemical polymerization and electrochemical doping polymerization. The experimental results show that the prepared Polyaniline films doped with sodium diphenylamine sulfonate have good electrochromic properties, such as uniform distribution, overall adhesion, fast response speed and good electrochromic properties. (2) six chiral 1,10-propanediol derivatives were synthesized, and the N * phase liquid crystals with the properties of thermal chiral inversion were induced by adding nematic liquid crystals. The N * phase liquid crystal with controllable pitch can be prepared by adjusting the proportion of the chiral derivatives with the characteristics of thermal chiral flipping and the composition of the chiral and dextral compounds. (3) the selection of fluoride matrix and co-doping of Er3 / Nd3 to adjust the competition between energy levels and the competitive relationship between radiative and non-radiative transitions is proposed. The fluorescence spectra of fluoride oxide glass and fluoride oxide glass ceramics verify the upconversion and mid-infrared luminescence properties of rare earth ions and improve the mid-infrared luminescence properties of Er3 doped ceramics. (4) Polyaniline-carbon nanotubes, polystyrene-C60 and polythiophene C60 complexes were prepared by in situ polymerization and emulsion polymerization. 40ps pulse Z- scan experiments show that the four composite samples have strong nonlinear absorption and optical limiting properties. The optical limiting mechanism of fullerene C60 based composites is nonlinear reverse saturation absorption of single excited state, and the optical limiting mechanism of carbon nanotube based composites is nonlinear absorption and induced scattering. The interaction between conjugated systems is of great significance in enhancing nonlinear optical properties and optical limiting properties. The suspension was prepared from graphene and single-walled carbon nanotubes, and the pulse width laser limiter experiment was carried out for 532nmP1064nm / 10ns. The results show that the sample suspensions have wideband limiting performance to ns pulse lasers. The series optical limiter is fabricated by using SWNTs-NMP and G-CB with different limiting thresholds, respectively. The optical limiting performance of ultra-low threshold and high damage threshold is realized. The optical limiting of graphene and single-walled carbon nanotube suspensions is a mechanism of absorption induced scattering.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TB34

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