利用電致選擇性氣相沉積製程技術製備表面奈米圖案化結構

A Fabrication Approach toward Surface Nanostructures Based on Electrically-Charged Selectivity of Chemical Vapor Deposition

謝洪斌(Hung-Pin Hsieh)

指導教授 ： 陳賢燁

國立臺灣大學/工學院/化學工程學研究所/碩士(2017年)

https://doi.org/10.6342/NTU201701136

摘要

本研究藉由施加電流的方式，來抑制多種不同功能性聚對二甲苯高分子(functional poly-para-xylene)沉積，且藉由結合奈米微影球技術，使用聚苯乙烯奈米球當作遮罩，製備出蜂窩狀的金屬圖案，搭配電源供應器設備施加0.1 A之電流，與不同之氬氣流速控制，成功於非金屬區域沉積上不同功能性聚對二甲苯高分子，與金屬區域抑制不同功能性聚對二甲苯高分子沉積，形成高度100nm 左右的不同樣貌之圓柱結構圖樣。首先，為了驗證電抑制的效果，我們在沉積的過程中，同時放入為施加電流的基材作為對照組，結束後使用傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometers, FTIR)分析基材上之表面官能基，驗證電抑制的效果。在成功沉積出奈米圓柱結構後，為了驗證製備出的奈米結構高分子，我們使用掃描式電子顯微鏡(scanning electron microscope,SEM)與原子力顯微鏡(atomic force microscope, AFM)觀察其表面型態，另外使用AFM內的分析軟體分析其粗糙度。為了探討表面不同官能基奈米結構高分子對於親疏水性質之改變，使用儀接觸角量測儀(Contact Angle Meter)。在確定表面物理性質後，為了探究其表面官能基的存在性，利用SME上之能量色散X-射線光譜(Energy-dispersive X-ray spectroscopy,EDS)進行特定元素分析。最後，在確定其特定官能基元素時，我們使用Alexa Fluors 350與FITC-RRCC分別對PPX-amine與PPX-TFA進行化學反應，利用超解析多光子光譜顯微鏡進行奈米圖案螢光影像擷取，以代表其官能基之化學反應活性。

未來，這項技術是由下而上的方式製備出奈米結構，成功突破了以往光罩上的清晰度與材料曲度上的限制，因此未來在任何曲面材料上形成具有功能之奈米結構更是輕易。聚對二甲苯具有良好的透光性，對於現今的鈣鈦礦(perovskite)太陽能電池具有極大的效用，利用奈米結構增加二氧化鈦上之PbI2與MAI之接觸面積，以提升轉化效率，進而提升太陽能電池光電轉換效率。材料端上，可透過一系列化學反應，將不同功能性之聚對二甲苯製備成導電高分子，以滿足未來可繞式裝置上太陽能電池之軟性需求。

關鍵字

化學氣相沉積 ； 電致選擇性氣相沉積製程技術 ； 功能性聚對二甲苯 ； 奈米結構圖樣 ； 表面改質

並列摘要

In this paper, a variety of functional poly-para-xylylene films were inhibited deposition by applying current. The metal patterns of honeycomb were manufactured with process of nanosphere lithography, which removing the polystyrene by tetrahydrofurane(THF) after using the nanospheres of polystyrene as a mask to deposits the metal. After the device were finished, a power supply device was set as 0.1 A and different argon flow rate in the chemical vapor deposition(CVD) was applied to form the nanostructure pattern of functional poly-para-xylylene with the height of about 100nm. First, in order to verify the effect of the electrically-charged selectivity, we placed the substrate and the control group with no current applied during the deposition process. Then, the surface functional groups of the substrate and the control groups were analyzed by fourier transform infrared spectrometers(FTIR) to verify the effect of electrical deposition inhibition. In order to verify the prepared nanostructured polymers, we observed the surface morphology by scanning electron microscope(SEM) and atomic force microscope(AFM). In addition, the roughness was analyzed by AFM analysis software. The change of hydrophobicity of different functional groups of nanostructures on the surface was investigated with the contact angle meter. For exploring the functional groups presence of its surface pattern, the specific elemental analysis was performed by energy-dispersive X-ray spectroscopy(EDS) on SME. Finally, the specific functional group elements were determined. To verify the chemical reactivity of its functional groups, we used the Alexa Fluors 350 and FITC-RRCC to react with PPX-amine and PPX-TFA, respectively. The ultra-analytical multi-photon spectroscopy was used to capture the nanopattern fluorescence image.

The technology of nano-structure by the bottom-up approaches successfully broke the restrictions of the clarity for mask and curved surface of material. Therefore, it is easy to form a functional nano-structure for any surface material in the future. For the properties of the material, the poly-para-xylene has good light transmittance and great utility to the perovskite solar cells. The use of nanostructures increases the contact area between PbI2 and MAI on titanium dioxide to enhance the conversion efficiency, thereby enhancing the efficiency of solar cell photoelectric conversion. A variety of functional poly-para-xylene can be prepared into a conductive polymer through a series of chemical reactions. It could be a potential candiadate material for flexible device for the solar cells.

並列關鍵字

chemical vapor diposition ； electrically-charged selectivity technology of chemical vapor deposition technology ； functional poly-para-xylylene ； nanostructured pattern ； surface modification

參考文獻

1.Chen, Y. and A. Pepin, Nanofabrication: Conventional and nonconventional methods. Electrophoresis, 2001. 22(2): p. 187-207.

2.Beccalli, A., et al. Demonstration of production readiness of an immersion lithography cell. in SPIE Advanced Lithography. 2008. International Society for Optics and Photonics.

3.Cole, M.A., et al., Stimuli-responsive interfaces and systems for the control of protein–surface and cell–surface interactions. Biomaterials, 2009. 30(9): p. 1827-1850.

4.Stevens, M.M. and J.H. George, Exploring and engineering the cell surface interface. Science, 2005. 310(5751): p. 1135-1138.

5.Sun, T., et al., Functional biointerface materials inspired from nature. Chemical Society Reviews, 2011. 40(5): p. 2909-2921.