碳黑分散劑之合成與黑色矩陣之微影圖案製作

Abstract

本研究的目的是為了合成出碳黑分散劑，改善碳黑於有機溶劑(PGMEA)中的聚集情況，並希望能應用於黑色矩陣的製備上。主要可以分為三個部份：分散劑的合成、碳黑的分散效果、以及實際應用於製備黑色矩陣。 首先是利用活性自由基聚合法來合成高分子，能精確控制聚合物的分子量及結構。我們以TEMPO為穩定自由基，加入Styrene、HEMA、DMAEMA與EHA等單體反應，製備出具有胺基與氫氧基的雜亂共聚合物PSDH，以及兩段式共聚合物(A-B型) PSEH-PSEHD與PSEH-b-PD。再由聚合物上的氫氧基與含異氰酸酯之壓克力單體進行接枝反應，可進一步合成出含不飽和雙鍵之碳黑分散劑。 在對碳黑的分散上，分散劑需要具有DMAEMA的三級胺幫助吸附在碳黑表面，才具有分散效果。雜亂共聚合物PSDH在接枝不飽和雙鍵之後，能由接枝的短側鏈去提供較好的立體阻礙效果，而使碳黑能分散到110nm左右；只是分散劑的添加量需要到碳黑的30wt%才行，不利於之後配製黑色矩陣光阻溶液。 使用兩段式共聚合物的PSEH-PSEHD或PSEH-b-PD，則只需要碳黑的15~20wt%即可使碳黑分散，碳黑粒徑最好可被分散到90~100nm；不過PSEH-b-PD由於DMAEMA段的極性較強，會使碳黑聚集，需再加入含酸基的樹脂，才能改善碳黑的聚集。而含不飽和雙鍵的PSEHｃ=ｃ-PSEHD或PSEHｃ=ｃ-b-PD，可能由於接枝的urethane造成部分架橋效應，碳黑會稍有聚集；若再加入樹脂則還有可能再聚集得更嚴重，但最好還是能使碳黑分散到110nm左右。 分散效果良好的碳黑，加入樹脂配製成光阻溶液後，經過塗佈、曝光、顯影的程序，就可以製備出黑色矩陣。目前使用兩段式共聚合物已可以製備出膜厚約1μm，光學密度3.5左右的黑色矩陣。

In order to prevent the coagulation of carbon black in organic solvent (PGMEA), this work was to synthesize a carbon black dispersant. Further, it can be used in the preparation of resin black matrix (RBM). There are three parts in this study: synthesis of dispersant, dispersion of carbon black, and the preparation of RBM. First, styrene, HEMA, EHA, and DMAEMA were used to synthesize random and block copolymers containing amino and hydroxyl group via nitroxide mediated polymerization. Therefore, we can control the molecular weight and the structure of polymers. The unsaturated vinyl group could be introduced into polymer by the reaction of isocyanate with hydroxyl group and the UV-curable carbon black dispersant could be obtained. The tertiary amine of DMAEMA in the copolymers can be anchoring group of carbon black. The dispersant, PSDHc=c, can provide more steric barrier, and the carbon black can be dispersed to around 110nm. However, the dispersant addition must be 30wt% of carbon black, it’s too high for the application of preparing RBM. The diblock copolymer (A-B type) PSEH-PSEHD or PSEH-b-PD can also be used as dispersant. The addition of these A-B type dispersant need only 15~20wt% of carbon black, and carbon black can be dispersed to 90~100nm. But the PSEH-b-PD with DMAEMA homopolymer, which have higher polarity, will lead to aggregation of carbon black. We have to add some resin with acid group and the carbon black dispersion can be approved. Because the dispersants with unsaturated vinyl group, which have urethane group, may lead to some bridge of particles, the carbon black will aggregate. If add resin, the aggregation will more critical. However, the carbon black still can be dispersed to around 110nm. By using A-B type dispersant, the carbon black will be dispersed well and can be used to preparing RBM. The film thickness of prepared RBM is 1μm, and optical density (OD) is around 3.5.