CN1273540C - 含铁电纳米晶的电光极化聚合物及其制备方法 - Google Patents
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Abstract
含铁电纳米晶的电光极化聚合物及其制备方法:铁电纳米晶均匀分布在透明的薄膜聚合物内。铁电纳米晶材料:铌酸锶钡、锆钛酸铅、掺镧的锆钛酸铅、钛酸钡BaTiO3,铌酸锂LiNbO3或钽酸锂LiTaO3,纳米晶粒径为20~80nm。聚合物基体材料:聚甲基丙烯酸甲酯(PMMA)、聚碳酸酯(PC)、和聚酰亚胺类和热塑性聚酰胺酸。可以在聚合时将铁电纳米晶共聚在聚合物内。亦可以将聚合物基体材料溶解在极性溶剂内,再将铁电纳米晶的前体溶液与此溶剂混和,再以甩胶法或浸渍法沉积薄膜。本发明通过将无机的铁电纳米晶和有机聚合物进行复合,既具有较大的电光系数,又具有优异的线性电光品质电光极化聚合物复合薄膜。
Description
一、技术领域
本发明涉及含铁电纳米晶的电光极化聚合物及其制备方法。
二、背景技术
极化聚合物是具有宏观二阶非线性的聚合物材料,具有快的响应时间、易修饰、易集成、易加工等特点,在集成光电子器件和光子器件中有重要的应用。近几年来,WDM(波分复用)全光网迅速发展,光开关的速度成为制约光通信发展的瓶颈问题,这使得极化聚合物材料成为WDM开发中的关键材料。目前研究成熟的机械开关、声光开关和以铌酸锂为代表的无机波导开关,由于响应速度慢、制作困难和不易集成等,限制了其长远应用。而电光极化聚合物具有的响应速度快、介电常数小等优点,使其在波导开关领域最有希望达到全光网传播的速度要求。
铁电材料SrxBa1-xNb2O6(SBN),Pb(ZrxTi1-x)O3(PZT)和(Pb1-yLay)(ZrxTi1-x)O3(PLZT)具有较大的电光系数,然而生长大的、完美的SBN、PZT单晶十分困难。铌酸锶钡(SrxBa1-xNb2O6,x=0.25-0.75,SBN)等晶体这方面的应用有待于发掘。
三、发明内容
本发明的目的是:提供一种含铁电纳米晶的电光极化聚合物及其制备方法。尤其是将适量的无机的铁电纳米晶和有机聚合物进行复合成含铁电纳米晶的电光极化聚合物,既利用了无机材料较大的电光系数,又利用了聚合物介电常数小和易集成、加工方便的优点,制备出具有较大的电光效应和优异的线性电光品质因子复合极化聚合物薄膜,且光损耗较低,在电光器件上具有切实可行的应用前景。
含铁电纳米晶的电光极化聚合物及制备方法:
含铁电纳米晶的电光极化聚合物:含铁电纳米晶均匀分布在透明的薄膜聚合物内。铁电纳米晶材料:铌酸锶钡(SrxBa1-xNb2O6,x=0.25-0.75,SBN),锆钛酸铅(Pb(ZrxTi1-x)O3,x=0-0.94,PZT),掺镧的锆钛酸铅(Pb1-yLay)(ZrxTi1-x)O3,y=0.02-0.30,x=0-1.00,PLZT),钛酸钡BaTiO3,铌酸锂LiNbO3和钽酸锂LiTaO3.纳米晶粒径为20~80nm。聚合物基体材料:聚甲基丙烯酸甲酯(PMMA)、聚碳酸酯(PC)、和聚酰亚胺类(如商业可获得的聚酰胺酸LQ-2200或PIQ-2200(Hitachi)体系和热塑性聚酰胺酸Ultradel 4212或3112体系)。
可以在聚合时将含铁电纳米晶共聚在聚合物内。亦可以将聚合物基体材料溶解在极性溶剂内,再将铁电纳米晶的前体溶液与此溶剂混和,再以甩胶法(spin-coating)或浸渍法(dip-coating)沉积薄膜,蒸发溶剂即可。尤其是在单晶硅片或镀铂的硅片,商业ITO导电玻璃,或石英玻璃等衬底材料上进行复合聚合物薄膜制备:用甩胶法(spin-coating)或浸渍法(dip-coating)沉积薄膜,并用普通热处理或真空热处理蒸发溶剂,温度60-100℃。重复这一工艺,获得所需的薄膜厚度。薄膜厚度在0.2~100微米。
为保证效果,对复合聚合物薄膜极化:在聚合物玻璃化温度附近,电晕极化,极化电压2~20千伏。
发明效果:通过将适量的无机的铁电纳米晶和有机聚合物进行复合,制备出既具有较大的电光系数(20-60pm/V),又具有优异的线性电光品质因子F2=n7γ2/ε(1000~10000)电光极化聚合物复合薄膜,且光损耗较低(0.3~3dβ/cm),兼具无机材料和有机聚合物的优点,制备工艺与集成光电子和集成光学工艺兼容,且成本较低,特别是在电光器件上具有较强的应用前景。
四、附图说明
图1为本发明含铁电纳米晶的电光极化聚合物结构示意图
图2水热法合成的PZT纳米晶超细粉末。
图3PZT/PC双折射率(Δn)与外加电场强度的关系。
图4本发明BaTiO3/PC复合聚合物薄膜和BaTiO3纳米粉末的X射线衍射图。
五、具体实施方式
铁电纳米晶材料的选择:铁电纳米晶材料:铌酸锶钡(SrxBa1-xNb2O6,x=0.25-0.75,SBN),锆钛酸铅(Pb(ZrxTi1-x)O3,x=0-0.94,PZT),掺镧的锆钛酸铅(Pb1-yLay)(ZrxTi1-x)O3,y=0.02-0.30,x=0-1.00,PLZT),钛酸钡BaTiO3,铌酸锂LiNbO3均是同时具有较大的电光系数(20-60pm/V)的材料。本发明利用其具有较大的电光系数制成专用材料。
铁电纳米晶通过前体溶液制备,将聚合物基体材料溶解在极性溶剂内,前体溶液和极性溶剂在单晶硅片或镀铂的硅片,商业ITO导电玻璃,或石英玻璃等衬底材料上进行复合聚合物薄膜制备:以甩胶法(spin-coating)或浸渍法(dip-coating)沉积薄膜,用普通热处理或真空热处理蒸发溶剂,温度60-100℃。
重复这一工艺,获得所需的薄膜厚度。薄膜厚度在0.2~100微米。
铁电纳米晶制备:水热法或溶胶-凝胶水解法,纳米晶的尺寸范围20-200纳米。前体溶液的制备:铁电纳米晶通过超声均匀分散在聚合物基体的氯仿溶液中,铁电纳米晶的浓度在1-30%(铁电纳米晶质量/聚合物基体的质量)。
例如:1.锆钛酸铅/聚碳酸酯(PZT/PC,Pb(Zr0.52Ti0.48)O3)体系,采用水热法获得粒径40~50nm的PZT纳米晶超细粉末(见图2),超声分散在PC的氯仿溶液中,在ITO导电玻璃衬底上,甩胶法制备PZT/PC复合聚合物薄膜,薄膜的厚度为1.2μm,PZT纳米晶的浓度为1Owt%。在8千伏,170℃的电晕极化后,室温下,PZT/PC双折射率(Δn)与外加电场强度的关系见图3。由此算得PZT/PC复合膜的有效电光系数为γ=30pm/V,线性电光品质因子F2=n7γ2/ε为~9000。光损耗小于1dβ/cm。
2.钛酸钡/聚碳酸酯体系(BaTiO3/PC),采用水热法获得粒径50nm的BaTiO3纳米晶超细粉末,超声分散在PC的氯仿溶液中,在ITO导电玻璃衬底上,甩胶法制备BaTiO3/PC复合聚合物薄膜,其X射线衍射见图4,表明复合膜基体中均匀分布着纯BaTiO3纳米晶相。薄膜的厚度为2μm,BaTiO3纳米晶的浓度为20wt%。在10千伏,160℃的电晕极化条件下,BaTiO3/PC复合膜的有效电光系数为γ=34pm/V,线性电光品质因子F2=n7γ2/ε为~10000。光损耗小于3dβ/cm。
3、锆钛酸铅/PIQ-2200(PZT/PIQ-2200,Pb(Zr0.52Ti0.48)O3)体系,选用强极性的溶剂,如N-甲基吡咯烷酮、DMF(二甲基甲酰胺),其余同1类似。
4、钛酸钡/PIQ-2200(BaTiO3/PIQ-2200)体系,选用强极性的溶剂,如N-甲基吡咯烷酮、DMF(二甲基甲酰胺),其余同2类似。例3、4类的聚酰胺酸或聚酰亚胺的材料的物理特性更加优异。
5、更容易制作是是锆钛酸铅/PMMA和钛酸钡/PMMA等系列,与1、2的工艺类似。
本发明用掺镧的锆钛酸铅PLZT、钛酸钡BaTiO3,铌酸锂LiNbO3或钽酸锂LiTaO3均可有类似性质,但其线性电光光损耗不同,关键是选用合适的粒径和分散均匀的纳米晶超细粉末。
Claims (6)
1、含铁电纳米晶的电光极化聚合物,其特征是铁电纳米晶均匀分布在透明的薄膜聚合物基体材料内;含铁电纳米晶材料为:铌酸锶钡SBN,锆钛酸铅PZT,掺镧的锆钛酸铅PLZT,钛酸钡BaTiO3,铌酸锂LiNbO3或钽酸锂LiTaO3,铁电纳米晶粒径为20~80nm;聚合物基体材料为:聚甲基丙烯酸甲酯PMMA、聚碳酸酯PC、或聚酰亚胺类。
2、含铁电纳米晶的电光极化聚合物的制备方法,其特征是将聚合物基体材料溶解在极性溶剂内,再将铁电纳米晶的前体溶液与此溶剂混和,再以甩胶法或浸渍法沉积薄膜,蒸发溶剂即可。
3、由权利要求2所述含铁电纳米晶的电光极化聚合物的制备方法,其特征是在单晶硅片或镀铂的硅片,ITO导电玻璃或石英玻璃衬底材料上进行复合聚合物薄膜制备。
4、由权利要求2所述含铁电纳米晶的电光极化聚合物的制备方法,其特征是蒸发溶剂的温度60-100℃。
5、由权利要求2所述含铁电纳米晶的电光极化聚合物的制备方法,其特征是重复甩胶法或浸渍法沉积薄膜,蒸发溶剂,获得所需的0.2~100微米的薄膜厚度。
6、由权利要求4所述含铁电纳米晶的电光极化聚合物的制备方法,其特征是对复合聚合物薄膜极化:在聚合物玻璃化温度附近,电晕极化,极化电压2~20千伏。
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CN110917906B (zh) * | 2019-12-11 | 2021-07-30 | 南京大学 | 一种铁电纳滤膜材料、制备方法及应用 |
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