本研究以二維發色團9-Hexyl-3,6- di(2’-(6-hydroxyhexyl) sulfonylphenyl)-1’-ethenyl)-9H-carbazole (Cz2PhSO2OH)及一維發色團4-N,N-Bis(2-hydroxyethylene) amine -4’- nitroazobenzene (DR19) 進行反應型溶凝膠反應,比較維度對非線性光學穩定性的影響。並以二維發色團9-Hexyl-3,6-di(2-(6-hexyl) sulfonyl phenyl)-1’-ethenyl) -9H– carbazole (Cz2PhSO26C)與Cz2PhSO2OH比較賓主型及反應型對二維發色團在無機基材中穩定性的影響。實驗結果證實反應型二維發色團溶/凝膠系統於二氧化矽高分子網狀結構的補強下,時間及動態熱穩定性有大幅提升的現象,於100℃下無SHG訊號衰退。並透過固態矽譜得知,在二維反應型溶/凝膠系統中,有效轉移溫度(T0)會隨溫度及時間的增加而提升,然而,二階諧波係數(d33)卻有一最適值;另外,經由極化條件的控制,使二維及一維發色團在相同交聯程度條件下進行反應,結果顯示二維反應型溶/凝膠系統的動態熱穩定性(T0=110℃)明顯較一維反應型溶/凝膠系統(T0=80℃)高。而且,此兩系統在各自的有效轉移溫度下觀察其隨時間變化的鬆弛行為,二維系統維持的有效二階諧波係數(65%)較一維系統(30%)的多;再者,二維賓主型溶/凝膠系統在極化過程中會發生昇華現象,這是由於發色團與基材無化學鍵結作用力。
Two dimensional (2D) chromophore, 9-Hexyl-3,6-di (2’-(6-hydroxy hexyl)sulfonylphenyl)-1’-ethenyl)-9H-carbazole(Cz2PhSO2OH), and one dimensional (1D) chromophore 4-N,N-Bis(2- hydroxy ethylene) amine-4’- nitroazobenzene (DR19) with two reactive site proceeded sol-gel process were studied to compare the effects between dimension of chromophore and nonlinear optical (NLO)stability. Hybrid NLO film with another 2D chromophore,9-Hexyl-3,6-di(2’-(6-hexyl)sulfonylphenyl)-1’-ethenyl) -9H– carbazole (Cz2PhSO26C) ,was studied to compare the influence between physical and chemical bonding. The results show that due to the reinforcement of SiO2 polymeric structure , hybrid NLO films with covalent-bonded 2D chromophore were highly improved in temporal and thermal dynamic stability. There is no decay in second harmonic coefficient (d33) at 100℃ for 200 hr. Effective transition temperature (T0) was raised with the enhancement of temperature and time by means of increasing degree of cross-linking , though d33 owns an optimal value. Moreover, by controlling the poling condition, the degree of cross-linking of SiO2 matrix with 2D and 1D chromophore is identical. As for thermal dynamic stability, NLO films with 2D chromophore (T0 = 110℃) are obviously better than with 1D chromophore (T0 = 80℃). As for temporal stability, effective second order harmonic coefficient (deff) of NLO film with 2D chromophore (65%) is better than with 1D chromophore (30%) under individual effective transition Temperature. For hybrid NLO film, the 2D chromophore would be sublimed during poling process since no chemical bondings between chromophore and matrix.