基于纳米压印技术构筑导电高分子图案
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摘要
在过去的几十年里,导电高分子图案已经被应用于场效应转换器、发光二极管、集成电路及传感器等许多领域。亚微米/微米级分辨率的导电高分子图案由于其特殊性能,近些年来备受瞩目。但是,目前用于在大面积上快速、低价构筑导电高分子图案的方法并不多,因而发展符合上述要求的导电高分子图案的构筑方法对导电高分子图案的广泛应用具有重要意义。
为了发展在大面积上快速、低价构筑导电高分子图案的方法,在本文中我们主要围绕以下两个方面展开讨论:
(1)我们详细讨论了纳米压印过程中,使用沟槽宽/深比较大的模板,在较薄阻挡层上不完全压印过程的细节,利用这种压印方法,我们实现了用低分辨率的模板构筑高分辨率图案;将这种不完全压印方法和均向刻蚀相结合,我们制备出了高分辨率的导电高分子图案,该图案的分辨率与使用的模板相比提高了近10倍,降低了图案的制备成本;以这种高分辨率的聚苯胺图案为模板,通过静电组装方法,我们使银纳米粒子选择性的沉积在聚苯胺表面,制备了高分辨率的复合图案。
(2)基于自组装聚苯乙烯胶体球阵列,我们可以制备周期不同的互补图案聚合物压印模板。选用不同直径的聚苯乙烯胶体球,我们构筑了周期不同的PMMA图案,结合导电高分子共聚沉积,得到了不同周期的聚苯胺点阵;通过控制PMMA图案的刻蚀时间,我们还可以得到直径不同的聚苯胺点阵。此外,我们还制得与点阵互补的聚苯胺网状图案。
总体来讲,本文主要介绍了两种在大面积上构筑导电高分子图案的巧妙方法,为大量低成本构筑导电高分子图案,提供了新的解决途径。
In the past decades, conducting polymer patterns have been employed in many different kinds of devices, such as field-effect transistors (FETs), light emitting diodes, integrated circuits, and sensors. And the patterns with the feature sizes of sub-micrometer to nanometer have recently received much attention because of their unique properties. To fabricate the conducting polymer patterns, various approaches, including photochemical patterning, microcontact printing (μCP), scanning probe lithography (SPL), electron-beam lithography (EBL), and many other methods have been proposed. However, scientists are still searching for the cost-efficient method for patterning conducing polymers with high resolution on large area.
For its relative low cost, high throughput, high reproducibility, and enviable resolution of a few nanometers over large area, nanoimprint lithography has been used for pixeled color structures, light emitting devices, electronic device and other devices. Comparing with the aforementioned methods, nanoimprint lithography has made a large progress in patterning. However, the cost and the lifetime of the stamp are still restricting the spread of the technique, which requires a good many efforts.
In this thesis, we aimed on the development of the conducting polymer patterning methods which are both simple and cost-effective. The works accomplished are listed as follows:
Firstly, the nanoimprint course was studies in detail. Although there have been a lot of papers focused on the nanoimprint course, no one have been exactly discussed the course when the stamp is with large cavity and small depth, while the resist polymer is relatively thin. Based on the phenomena we found, the inadequate imprinting course was well discussed. And the high resolution patterns were fabricated by low resolution stamp.
Secondly, by the combination of inadequate imprinting and the isotropic etching, high resolution conducting polymer patterns were fabricated by low resolution stamps. The resolution of the conducting polymer patterns are exactly controllable by designing the imprinting and etching course. Moreover, the property of the conducting polymer pattern was well kept, with a most improvement on the resolution of ten times. A cost-effective imprinting method was proposed.
Thirdly, to exploit the usage of the conducting polymer patterns on the biosensors, by using the polyaniline pattern as the templete and controlling the deposition condition, the Silver nanoparticles were selectively adsorbed on the polyanilane patterns by the electrostatic interaction, and the combined patterns with high resolution were constructed.
Fourthly, based on the PS colloid sphere self-assembling technique, we fabricated polymer stamps which are suitable for hot embossing nanoimprint. It is worthy to mention that both the stamps with positive and negative patterns were fabricated by one stamp fabrication course. PMMA patterns with different periodicity were fabricated by the utilization of PS colloid spheres with different diameters. And by using conducting polymer deposition, polyanilane dot arrays with different periodicity were constructed. Further more, modulating the PMMA pattern etching duration, the diameter of the polyanilane dot was controlled. Moreover, polyanilane network patterns were fabricated by the negative patterned stamp.
In conclusion, two smart large area conducting polymer patterning methods were introduced in this thesis. Avoiding the high cost of the stamp fabrication, new cost-effective strategies were illustrated for the fabrication of conducting polymer patterns over large area.
为了发展在大面积上快速、低价构筑导电高分子图案的方法,在本文中我们主要围绕以下两个方面展开讨论:
(1)我们详细讨论了纳米压印过程中,使用沟槽宽/深比较大的模板,在较薄阻挡层上不完全压印过程的细节,利用这种压印方法,我们实现了用低分辨率的模板构筑高分辨率图案;将这种不完全压印方法和均向刻蚀相结合,我们制备出了高分辨率的导电高分子图案,该图案的分辨率与使用的模板相比提高了近10倍,降低了图案的制备成本;以这种高分辨率的聚苯胺图案为模板,通过静电组装方法,我们使银纳米粒子选择性的沉积在聚苯胺表面,制备了高分辨率的复合图案。
(2)基于自组装聚苯乙烯胶体球阵列,我们可以制备周期不同的互补图案聚合物压印模板。选用不同直径的聚苯乙烯胶体球,我们构筑了周期不同的PMMA图案,结合导电高分子共聚沉积,得到了不同周期的聚苯胺点阵;通过控制PMMA图案的刻蚀时间,我们还可以得到直径不同的聚苯胺点阵。此外,我们还制得与点阵互补的聚苯胺网状图案。
总体来讲,本文主要介绍了两种在大面积上构筑导电高分子图案的巧妙方法,为大量低成本构筑导电高分子图案,提供了新的解决途径。
In the past decades, conducting polymer patterns have been employed in many different kinds of devices, such as field-effect transistors (FETs), light emitting diodes, integrated circuits, and sensors. And the patterns with the feature sizes of sub-micrometer to nanometer have recently received much attention because of their unique properties. To fabricate the conducting polymer patterns, various approaches, including photochemical patterning, microcontact printing (μCP), scanning probe lithography (SPL), electron-beam lithography (EBL), and many other methods have been proposed. However, scientists are still searching for the cost-efficient method for patterning conducing polymers with high resolution on large area.
For its relative low cost, high throughput, high reproducibility, and enviable resolution of a few nanometers over large area, nanoimprint lithography has been used for pixeled color structures, light emitting devices, electronic device and other devices. Comparing with the aforementioned methods, nanoimprint lithography has made a large progress in patterning. However, the cost and the lifetime of the stamp are still restricting the spread of the technique, which requires a good many efforts.
In this thesis, we aimed on the development of the conducting polymer patterning methods which are both simple and cost-effective. The works accomplished are listed as follows:
Firstly, the nanoimprint course was studies in detail. Although there have been a lot of papers focused on the nanoimprint course, no one have been exactly discussed the course when the stamp is with large cavity and small depth, while the resist polymer is relatively thin. Based on the phenomena we found, the inadequate imprinting course was well discussed. And the high resolution patterns were fabricated by low resolution stamp.
Secondly, by the combination of inadequate imprinting and the isotropic etching, high resolution conducting polymer patterns were fabricated by low resolution stamps. The resolution of the conducting polymer patterns are exactly controllable by designing the imprinting and etching course. Moreover, the property of the conducting polymer pattern was well kept, with a most improvement on the resolution of ten times. A cost-effective imprinting method was proposed.
Thirdly, to exploit the usage of the conducting polymer patterns on the biosensors, by using the polyaniline pattern as the templete and controlling the deposition condition, the Silver nanoparticles were selectively adsorbed on the polyanilane patterns by the electrostatic interaction, and the combined patterns with high resolution were constructed.
Fourthly, based on the PS colloid sphere self-assembling technique, we fabricated polymer stamps which are suitable for hot embossing nanoimprint. It is worthy to mention that both the stamps with positive and negative patterns were fabricated by one stamp fabrication course. PMMA patterns with different periodicity were fabricated by the utilization of PS colloid spheres with different diameters. And by using conducting polymer deposition, polyanilane dot arrays with different periodicity were constructed. Further more, modulating the PMMA pattern etching duration, the diameter of the polyanilane dot was controlled. Moreover, polyanilane network patterns were fabricated by the negative patterned stamp.
In conclusion, two smart large area conducting polymer patterning methods were introduced in this thesis. Avoiding the high cost of the stamp fabrication, new cost-effective strategies were illustrated for the fabrication of conducting polymer patterns over large area.
引文
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