基于激光干涉技术的微纳结构制造研究
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摘要
在本论文中,我们研究了利用激光干涉制造不同微纳结构的方法。基于偶氮苯聚合物,研究了可控的微纳结构的制造方法。掌握了一些激光控制技术,制作了一系列不同微纳尺度的结构。本文的主要内容包括:
1.激光和偶氮苯聚合物材料相互作用研究。介绍了偶氮苯聚合物的种类和光致异构化的机理。详细分析了激光照射偶氮苯材料所导致的各种移动和对应的光响应性质,包括光致取向,光致质量迁移,光机效应等。然后重点介绍了光致取向的表征,测量方法。讨论了影响偶氮苯聚合物材料光响应性质的因素。研究了取代基,热交联和掺银纳米粒子对光致双折射的形成速度,幅度和可重复擦写性。实验结果表明,通过引入推拉电子基团(取代基)可以有效提高偶氮苯材料的光致响应速度和光致双折射的大小;热交联的方式可以有效抑制偶氮苯材料的光致质量迁移;研究了两种方法制作得到的银纳米粒子/偶氮苯聚合物复合材料的光响应性质,包括直接掺杂和原位还原得到的材料。
利用干涉技术制作周期和准周期的微纳结构若干问题研究。
利用多光束激光干涉技术在空间上可以形成周期或准周期分布的能量分布结构。通过参数控制,如相位控制,偏振态控制和能量配比可以调节干涉场单元结构的能量分布。偏振态控制的双光束全息干涉可以在偶氮苯材料中形成不同形式的光栅,如表面起伏光栅和纯折射率光栅。四光束以上的多光束干涉场能量分布受光束的相位和偏振态影响较大。三光束干涉的能量单元结构不受干涉光相位的影响,通过改变干涉光的偏振态组合可以得到不同的能量场分布,从而在材料上形成各种复杂的表面结构。通过双光束或三光束多曝光的技术可以在样品上制作多种准周期微纳结构。
光致偶氮苯聚合物材料质量迁移规律研究
基于高能量激光烧蚀,采用偏振控制三光束干涉技术在偶氮苯聚合物上制作得到的六角形分布的偶氮苯聚合物圆台结构。利用偏振全息技术调控空间的能量场和偏振分布,并照射圆形的偶氮苯聚合物产生凸起结构。(P, P)干涉模式下,圆形凸起结构沿着P偏振方向发生变形;(S, S)干涉模式下,圆形结构由于热效应在平面内没有发生变形;(+45°, -45°)和(S, P)干涉模式下,结构并不发生变形。采用单光束均匀能量照射时,圆形结构沿着光束的偏振方向发生变形。采用微透镜对光束聚焦的模型分析得到,单光束照射在微凸起结构内会形成能量梯度,且能量场分布关于中心对称。实验结果表明,照射光束的偏振矢量和能量梯度保持方向一致时,偶氮苯聚合物内发生光致质量迁移。
光致偶氮苯聚合物双尺度微纳结构形成研究。
从仿生学角度出发,双尺度结构在高疏水性,结构色和高吸附力等方面都具有潜在的应用。针对不同取代基(主要是氰基和甲基)的偶氮苯聚合物材料,采用干涉技术制造可控的双尺度结构。首先利用单光束照射技术在不同的偶氮苯聚合物材料制造单尺度纳米结构。实验结果表明在氰基聚合物材料上得到纳米级的带状液晶结构,其取向与照射光的偏振态保持一致;而甲基聚合物材料上只能得到纳米簇结构,簇的形态不受照射光的偏振态影响。利用干涉在偶氮苯聚合物上制作得到了具有纳米结构的微米周期结构,即形成双尺度微纳结构。纳米结构的大小,走向等可以通过控制干涉激光的偏振态,照射功率和照射时间进行控制。
矢量偏振光形成技术和性质研究。
基于高双折射C切钒酸钇晶体,我们得到了轴对称偏振光,包括径向偏振光和角向偏振光。采用C切钒酸钇晶体产生轴对称偏振光具有成本低,可以根据工作波长进行调节的优点,在实验应用中具有较强的可行性。基于波片对偏振的转换的原理和偶氮苯聚合物具有光致双折射的性质,我们设计并制作了轴对称相位延迟片。通过激光诱导在偶氮苯薄膜中形成轴对称分布的分子排列,得到相位延迟均匀,光轴轴对称分布的相位延迟片。这种相位延迟片可以通过改变材料的参数,如厚度、材料组分等,得到稳定的相位延迟,从而能够用于产生不同的轴对称偏振光。
In this thesis, the approaches of the fabrication of micro and nano structures are investigated. Several technologies of controlling laser beams are developed and applied to generate a series of surface patterns and volume structures. The contents of the thesis are as follows:
1. Investigation of the laser and azopolymer interactions.
The introduction of azopolymers and their properties are presented. Laser induced isomerization are introduced. The laser induced motions in different scales and the corresponding responsive properties, like photo-induced orientation, mass migration, photo-mechanics effect, are presented. The characterization and the measurement approach are discussed. Finally, azopolymer with different substituent groups, cross-linked degrees and composite polymer (azopolymer doped with Ag nano particles) are investigated by laser induced orientation. The experimental results illustrate that substituent group has strong influence upon the orientation of azopolymer. Cross-linking will suppress mass migration inside azopolymer. Azopolymer doped with Ag nano particle will quicken the orientation of the composite material in low consistency intermingle, while the orientation speed will be slacked off in high consistency intermingles. Ag nanoparticle/azopolymer nanocomposites are prepared with controlled concentration of Ag nanoparticles by in situ reduction of Ag(I)–diketone complexes in an azopolymer matrix. Compared with pure azopolymer, the birefringence of this nanocomposite is more stable.
2. Fabrication of periodic and quasi-periodic micro and nano structures via laser interference technologies. The multiple-beam interference technology is used to modulate the intensity distribution and the polarization states in the space by controlling the phase, the polarization and the intensity of the interfering beams. Via two-beam polarization holography, surface relief gratings and refractive index gratings are generated. Simulative results by Matlab illuminate that if the number of the interfering beams is above (including) four, the phase and the polarization of the interference have strong influence upon the interfering field. In three-beam interference case, the phase of the interfering beams will not change the shape of the intensity patterns. However, by controlling the polarization of the interfering beams, we can obtain different patterns in the interfering field, which can be applied to generate different textures. Multiple exposures of two-beam interference and three-beam interference can be utilized to generate quasi-periodic microstructures on different sample surface.
3. Investigation of the mechanism laser induced mass migration inside azopolymer materials. Hexagonally distributed circular caps are generated on the surface of azopolymer films by polarization controlled three-beam interference ablation and utilized as the investigated objectives to demonstrate the mechanism of laser induced mass migration inside azopolymer materials. Two beam interference of different polarization arrangements are adjusted and used to expose the circular caps on azopolymers. While the interfering beams are of (P, P) mode, the caps are stretched along the direction of P polarization. If the interfering mode is set to (P, P) and (+45°, -45°), the caps are seldom deformed in the surface plane. When the interfering beams are of (S, P) mode, the caps are deformed in the tilted direction. The experimental results illuminate that only when the intensity gradient exists in the direction of the irradiating polarization, the mass migration happens inside azopolymers.
4. Fabrication of dual-scale structure on azopolymer. Dual-scale microstructures can be used as superhydrophobic surface, structural color and high adhesive surface. Based on laser interference technology, dual-scale microstructures can be fabricated on azopolymer surface. Two different materials four amorphous side chain azopolymers with cyano group (AzoCN), methyl group (AzoCH3) are used as investigated objectives. Experimental results illuminate that nano band textures will be formed on the surface of azopolymers with cyano group (AzoCN) when the sample is exposed by single beam exposure. However, only nano cluster structures will be formed on azopolymers with methyl group (AzoCH3). The size of the nano structures is dependent on the laser exposure dose and the laser power. While the sample are exposed to two beam interference of different modes, on AzoCN, dual-scale structures with nano textures in different directions can be formed, and on AzoCH3, dual-scale structures with nano cluster structuresare formed.
5. Generation of cylindrical vector beams. Cylindrical vector beams, like radially polarized beams and azimuthally polarized beams are generated by carefully selecting the output light of high birefringence C-cut YVO4 crystal. YVO4 crystal can be used produced cylindrical vector beams with different wavelengths. Based on azopolymer, we designed and produced axisymmetric phase retardation plates (ASPRP). The phase retardation of ASPRP can be easily controlled by materials, the thickness of the sample films and the laser dose. ASPRP can be used to generate cylindrical vector beams.
1.激光和偶氮苯聚合物材料相互作用研究。介绍了偶氮苯聚合物的种类和光致异构化的机理。详细分析了激光照射偶氮苯材料所导致的各种移动和对应的光响应性质,包括光致取向,光致质量迁移,光机效应等。然后重点介绍了光致取向的表征,测量方法。讨论了影响偶氮苯聚合物材料光响应性质的因素。研究了取代基,热交联和掺银纳米粒子对光致双折射的形成速度,幅度和可重复擦写性。实验结果表明,通过引入推拉电子基团(取代基)可以有效提高偶氮苯材料的光致响应速度和光致双折射的大小;热交联的方式可以有效抑制偶氮苯材料的光致质量迁移;研究了两种方法制作得到的银纳米粒子/偶氮苯聚合物复合材料的光响应性质,包括直接掺杂和原位还原得到的材料。
利用干涉技术制作周期和准周期的微纳结构若干问题研究。
利用多光束激光干涉技术在空间上可以形成周期或准周期分布的能量分布结构。通过参数控制,如相位控制,偏振态控制和能量配比可以调节干涉场单元结构的能量分布。偏振态控制的双光束全息干涉可以在偶氮苯材料中形成不同形式的光栅,如表面起伏光栅和纯折射率光栅。四光束以上的多光束干涉场能量分布受光束的相位和偏振态影响较大。三光束干涉的能量单元结构不受干涉光相位的影响,通过改变干涉光的偏振态组合可以得到不同的能量场分布,从而在材料上形成各种复杂的表面结构。通过双光束或三光束多曝光的技术可以在样品上制作多种准周期微纳结构。
光致偶氮苯聚合物材料质量迁移规律研究
基于高能量激光烧蚀,采用偏振控制三光束干涉技术在偶氮苯聚合物上制作得到的六角形分布的偶氮苯聚合物圆台结构。利用偏振全息技术调控空间的能量场和偏振分布,并照射圆形的偶氮苯聚合物产生凸起结构。(P, P)干涉模式下,圆形凸起结构沿着P偏振方向发生变形;(S, S)干涉模式下,圆形结构由于热效应在平面内没有发生变形;(+45°, -45°)和(S, P)干涉模式下,结构并不发生变形。采用单光束均匀能量照射时,圆形结构沿着光束的偏振方向发生变形。采用微透镜对光束聚焦的模型分析得到,单光束照射在微凸起结构内会形成能量梯度,且能量场分布关于中心对称。实验结果表明,照射光束的偏振矢量和能量梯度保持方向一致时,偶氮苯聚合物内发生光致质量迁移。
光致偶氮苯聚合物双尺度微纳结构形成研究。
从仿生学角度出发,双尺度结构在高疏水性,结构色和高吸附力等方面都具有潜在的应用。针对不同取代基(主要是氰基和甲基)的偶氮苯聚合物材料,采用干涉技术制造可控的双尺度结构。首先利用单光束照射技术在不同的偶氮苯聚合物材料制造单尺度纳米结构。实验结果表明在氰基聚合物材料上得到纳米级的带状液晶结构,其取向与照射光的偏振态保持一致;而甲基聚合物材料上只能得到纳米簇结构,簇的形态不受照射光的偏振态影响。利用干涉在偶氮苯聚合物上制作得到了具有纳米结构的微米周期结构,即形成双尺度微纳结构。纳米结构的大小,走向等可以通过控制干涉激光的偏振态,照射功率和照射时间进行控制。
矢量偏振光形成技术和性质研究。
基于高双折射C切钒酸钇晶体,我们得到了轴对称偏振光,包括径向偏振光和角向偏振光。采用C切钒酸钇晶体产生轴对称偏振光具有成本低,可以根据工作波长进行调节的优点,在实验应用中具有较强的可行性。基于波片对偏振的转换的原理和偶氮苯聚合物具有光致双折射的性质,我们设计并制作了轴对称相位延迟片。通过激光诱导在偶氮苯薄膜中形成轴对称分布的分子排列,得到相位延迟均匀,光轴轴对称分布的相位延迟片。这种相位延迟片可以通过改变材料的参数,如厚度、材料组分等,得到稳定的相位延迟,从而能够用于产生不同的轴对称偏振光。
In this thesis, the approaches of the fabrication of micro and nano structures are investigated. Several technologies of controlling laser beams are developed and applied to generate a series of surface patterns and volume structures. The contents of the thesis are as follows:
1. Investigation of the laser and azopolymer interactions.
The introduction of azopolymers and their properties are presented. Laser induced isomerization are introduced. The laser induced motions in different scales and the corresponding responsive properties, like photo-induced orientation, mass migration, photo-mechanics effect, are presented. The characterization and the measurement approach are discussed. Finally, azopolymer with different substituent groups, cross-linked degrees and composite polymer (azopolymer doped with Ag nano particles) are investigated by laser induced orientation. The experimental results illustrate that substituent group has strong influence upon the orientation of azopolymer. Cross-linking will suppress mass migration inside azopolymer. Azopolymer doped with Ag nano particle will quicken the orientation of the composite material in low consistency intermingle, while the orientation speed will be slacked off in high consistency intermingles. Ag nanoparticle/azopolymer nanocomposites are prepared with controlled concentration of Ag nanoparticles by in situ reduction of Ag(I)–diketone complexes in an azopolymer matrix. Compared with pure azopolymer, the birefringence of this nanocomposite is more stable.
2. Fabrication of periodic and quasi-periodic micro and nano structures via laser interference technologies. The multiple-beam interference technology is used to modulate the intensity distribution and the polarization states in the space by controlling the phase, the polarization and the intensity of the interfering beams. Via two-beam polarization holography, surface relief gratings and refractive index gratings are generated. Simulative results by Matlab illuminate that if the number of the interfering beams is above (including) four, the phase and the polarization of the interference have strong influence upon the interfering field. In three-beam interference case, the phase of the interfering beams will not change the shape of the intensity patterns. However, by controlling the polarization of the interfering beams, we can obtain different patterns in the interfering field, which can be applied to generate different textures. Multiple exposures of two-beam interference and three-beam interference can be utilized to generate quasi-periodic microstructures on different sample surface.
3. Investigation of the mechanism laser induced mass migration inside azopolymer materials. Hexagonally distributed circular caps are generated on the surface of azopolymer films by polarization controlled three-beam interference ablation and utilized as the investigated objectives to demonstrate the mechanism of laser induced mass migration inside azopolymer materials. Two beam interference of different polarization arrangements are adjusted and used to expose the circular caps on azopolymers. While the interfering beams are of (P, P) mode, the caps are stretched along the direction of P polarization. If the interfering mode is set to (P, P) and (+45°, -45°), the caps are seldom deformed in the surface plane. When the interfering beams are of (S, P) mode, the caps are deformed in the tilted direction. The experimental results illuminate that only when the intensity gradient exists in the direction of the irradiating polarization, the mass migration happens inside azopolymers.
4. Fabrication of dual-scale structure on azopolymer. Dual-scale microstructures can be used as superhydrophobic surface, structural color and high adhesive surface. Based on laser interference technology, dual-scale microstructures can be fabricated on azopolymer surface. Two different materials four amorphous side chain azopolymers with cyano group (AzoCN), methyl group (AzoCH3) are used as investigated objectives. Experimental results illuminate that nano band textures will be formed on the surface of azopolymers with cyano group (AzoCN) when the sample is exposed by single beam exposure. However, only nano cluster structures will be formed on azopolymers with methyl group (AzoCH3). The size of the nano structures is dependent on the laser exposure dose and the laser power. While the sample are exposed to two beam interference of different modes, on AzoCN, dual-scale structures with nano textures in different directions can be formed, and on AzoCH3, dual-scale structures with nano cluster structuresare formed.
5. Generation of cylindrical vector beams. Cylindrical vector beams, like radially polarized beams and azimuthally polarized beams are generated by carefully selecting the output light of high birefringence C-cut YVO4 crystal. YVO4 crystal can be used produced cylindrical vector beams with different wavelengths. Based on azopolymer, we designed and produced axisymmetric phase retardation plates (ASPRP). The phase retardation of ASPRP can be easily controlled by materials, the thickness of the sample films and the laser dose. ASPRP can be used to generate cylindrical vector beams.
引文
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