計畫編號：NSC96-2221-E032-032研究期間：200708~200807研究經費：780,000[[abstract]]本計畫擬研發新型顏料分散型彩色光阻，並應用於彩色濾光片之製 程。首先是以自由基聚合法合成Poly(BZMA-MAA-2HEMA)共聚合壓克力 樹脂作為光阻的結合劑，並量測酸價、黏度及熱性質；再以溶膠－凝膠法 製作表面改質之SiO2 奈米粒子，並結合有機－無機混成之概念，將其導入 高分子光阻系統中，此SiO2 粒子表面富含反應性之雙鍵，可與光阻中之感 光性多官能基單體反應而達成奈米混成效果，最後再加入顏料分散液，即 製備出顏料分散型彩色光阻。此改良型顏料分散型彩色光阻，預期將比傳 統型顏料分散型彩色光阻具有更佳的密著性、硬度及耐熱性等。材料分析 檢測則首先使用GPC 來鑑定結合劑分子量；以FTIR 分析光阻材料在製備 過程中，相關官能基之變化情形；光學性質方面則將量測彩色光阻之色度 座標及光穿透度；最後將材料進行TGA、DSC 及TMA 等熱分析的測試， 以瞭解Td、Tg 及熱膨脹係數之改善程度。[[sponsorship]]行政院國家科學委員

張正良

計畫編號：NSC96-2221-E032-032研究期間：200708~200807研究經費：780,000本計畫擬研發新型顏料分散型彩色光阻，並應用於彩色濾光片之製 程。首先是以自由基聚合法合成Poly(BZMA-MAA-2HEMA)共聚合壓克力 樹脂作為光阻的結合劑，並量測酸價、黏度及熱性質；再以溶膠－凝膠法 製作表面改質之SiO2 奈米粒子，並結合有機－無機混成之概念，將其導入 高分子光阻系統中，此SiO2 粒子表面富含反應性之雙鍵，可與光阻中之感 光性多官能基單體反應而達成奈米混成效果，最後再加入顏料分散液，即 製備出顏料分散型彩色光阻。此改良型顏料分散型彩色光阻，預期將比傳 統型顏料分散型彩色光阻具有更佳的密著性、硬度及耐熱性等。材料分析 檢測則首先使用GPC 來鑑定結合劑分子量；以FTIR 分析光阻材料在製備 過程中，相關官能基之變化情形；光學性質方面則將量測彩色光阻之色度 座標及光穿透度；最後將材料進行TGA、DSC 及TMA 等熱分析的測試， 以瞭解Td、Tg 及熱膨脹係數之改善程度。行政院國家科學委員

Tamkang University Institutional Repository

行政院國家科學委員會補助專題研究計畫 ■ 成 果 報 告   □期中進度報告  奈米二氧化矽改質負型壓克力彩色光阻之製備 Characterization of Acrylic Copolymers applied in Negative-Type Photoresist via a Ternary Composition Diagram 計畫類別：■ 個別型計畫  □ 整合型計畫 計畫編號：NSC 96-2221-E-032-032- 執行期間：2007 年 8 月 1 日至 2007 年 8 月 31 日  計畫主持人：張正良 共同主持人：鄭廖平 計畫參與人員：張誌民、陳志維    成果報告類型(依經費核定清單規定繳交)：■精簡報告  □完整報告  本成果報告包括以下應繳交之附件： □赴國外出差或研習心得報告一份 □赴大陸地區出差或研習心得報告一份 □出席國際學術會議心得報告及發表之論文各一份 □國際合作研究計畫國外研究報告書一份   處理方式：除產學合作研究計畫、提升產業技術及人才培育研究計畫、列管計畫及下列情形者外，得立即公開查詢           □涉及專利或其他智慧財產權，□一年□二年後可公開查詢           執行單位：淡江大學化學工程與材料工程學系  中   華   民   國    97 年    8 月    8 日 1   摘要  本研究成功合成三成份壓克力共聚高分子作為負型光阻之結合劑，並針對其各項性質進行檢測。本研究中首先以自由基聚合法製備雙成分結合劑，並針對其熱性質、黏度及分子量進行檢測。隨後在雙成份結合劑中加入另一單體以製備三成分結合劑。所製備之結合劑藉由FT-IR 進行化學結構之鑑定，並以 TGA 及 DSC 檢測材料之熱性質。最後可繪製三成分組成座標圖並利用所檢測之結果判定三成分結合劑的最佳組成比例。  關鍵詞：結合劑、三成分組成座標圖、負型光阻     ABSTRACT     Three-component acrylic copolymers used as a binder for negative-type photoresists were synthesized and characterized. First, free radical polymerization was employed to synthesize two-component binders, i.e., acrylic ester copolymers with different ratios of benzyl methacrylate (BZMA) and methacrylic acid (MAA). Thermal behavior, viscosity and molecular weight of the prepared two-component binders were studied. Then, a series of three-component binders were prepared through incorporation of another monomer, 2-hydroxyethyl methacrylate (2-HEMA). FTIR was used to examine the evolution of chemical bonds at various stages of the synthetic process. Thermal analyses, TGA and DSC, were used to evaluate the level of enhancement on thermal stabilities of the prepared three-component binders. Finally, an optimal region in the ternary composition diagram of BZMA, MAA, and 2-HEMA can be identified by comparing the results of acid value, viscosity and molecular weight of the binder.  Key words: binder; ternary composition diagram; negative-type photoresists1  INTRODUCTION Photoresist is generally a type of photosensitive polymer solution. The classification of photoresist is commonly based on the reaction mechanism during the exposure process [1-4]. If a positive-type photoresist is exposed to photo irridiation, the exposed area could be removed by dissolution in an alkaline developer liquid in the developing process. In contrast, the dissolved area of a negative-type photoresist is the unexposed area because the exposed area is crosslinked upon irradiation. After development, the desired circuit or pattern is formed on a substrate. Photoresists are widely used for the manufacture of microelectronics, silk screen printings, printed circuit boards, optical disks, color filter resists and so on [5-7]. Typically, a negative-type photoresist consists of polymer binder, photosensitive polyfunctional monomer, photoinitiator, solvents and additives [8,9]. Acrylic monomers used to synthesize the binder contain the desired functional groups, such as benzyl, hydroxyl, carboxyl groups, etc. The former two functional groups can improve both the dispersion of pigments and the adhesion of photoresist on glass substrate. On the other hand, carboxyl group can provide sufficient acid value of the prepared photoresist. However, it should be noted that when the content of polar functional groups, such as hydroxyl and carboxyl groups, is too high, the solubility of the synthesized binders in organic solvent decreases. A suitable amount of pigment may be added into the photoresist to form colored photoresist, which is termed pigment dispersant color resist (PDCR), and is applied to color filter formation. As a binder for industrial applications, there are several basic criteria that should be obeyed. For example, the acid value has to be lager than 100 mg KOH/g and the molecular weight be controlled in the range of 1.5~3.5×104 g/mol. Supposed that the binder is to be used for the manufacture of photoresist applied in color filter, the resolution should be less than 10 μm. In this research, a series of binders were synthesized by free radical copolymerization of three kinds of acrylic monomers (BZMA, MAA, and 2-HEMA), and their properties were studied to find the optimal compositions for the binder. More importantly, the optimal composition of the synthesized binders was determined using a ternary composition diagram. Following that a negative-type photoresist was prepared and its resolution was determined.  EXPERIMENTAL     Copolymer binders were prepared by free radical polymerization of three kinds of acrylate monomers, BZMA, MAA, and 2-HEMA in cyclohexanone (solid content = 40 wt%). The monomer solution was preheated at 100oC and stirred under nitrogen atmosphere. Then, initiator (AIBN, 1 wt% of total monomers) and chain-transfer agent (Thiol, 1 wt % of total monomers) dissolved in the same solvent were dropped slowly into the monomer solution. Free-radical polymerization was carried out for 6 h, and then the product was cooled down to room temperature. The obtained acrylate resin, poly(BZMA-MAA-2HEMA), was used as the binder of the photoresist. Binder samples were named according to the rule: the first letter of the monomer name followed by their respective compositions in molar percentage. To prepare samples for characterization of thermal  2property, acid value, or chemical structure, the formed binder solution was diluted with tetrahydrofuran (THF) and then poured into hexane to induce polymer precipitation. The precipitation procedure was repeated twice to ensure free of residual monomers. Finally, the white polymer precipitate were separated by filtration and then dried in vacuo at 60oC.  RESULTS AND DISCUSSION Three-component binders were prepared by incorporation of the third kind of acrylate monomer, 2-HEMA, in the synthesis process. Because of its hydroxyl group, 2-HEMA could enhance the adhesion between photoresist and glass substrate. However, viscosity of the prepared binder will increase as 2-HEMA content increases. In the discussion that follows, thermal behavior, viscosity, Mw and acid value of three-component binders were presented and compared. Compositions of the three monomers in the binder were illustrated in terms of a “ternary composition diagram” (cf. Fig.1 (▲)).   0.00.20.40.60.81.0 0.00.20.40.60.81.0 9:18:27:3Solution gelled2-HEMABZMAMAASolution gelled6:4Fig. 1 Ternary composition diagram of the prepared binders. (a) Thermal behaviors Glass transition temperatures (Tg) of pure poly(2-hydroxyethyl methacrylate) is 55oC, as obtained from the literature. Previous results of two-component binders showed that Tg increased with increasing MAA content. DSC thermograms of the three-component binders are shown in Fig. 2, and Tg values are collected in Table 1. It appears that Tg of the binders with the same BZMA/MAA ratio were very close to each other, regardless of the 2-HEMA content. Specifically, for the case of BZMA/MAA= 9:1, Tg of the four binders are all closed to 74oC. However, Tg of the B80M20H0 was still slightly higher than that of B56M14H30, ca. 1.4oC, due to the higher content of MAA. On the other hand, for samples of the same 2-HEMA content, Tg increased with increasing MAA content, in accordance with the previous results.   40 60 80 100 120 140 160 180Temperature (oC)B56M14H30B64M16H20B54M36H10B63M27H10B72M18H10B80M20H0Heat Flow (W/ g)   Fig. 2 DSC thermograms of several three-component binders.   TGA was utilized to measure the Td of the three-component binders. Because thermal decomposition behaviors of the three-component binders were complicate and  3involved several stages, the temperature corresponding to 10 wt% loss was identified as the thermal degradation temperature, Td10, for easy comparison. The results are listed in Table 1. Fig. 3 shows the TGA thermograms of several typical three-component binders, from which it can be seen that the thermal decomposition generally follows a three-stage pattern, which is consistent with the data shown in the literature. For all samples, the first-, second- and the third-stage occurred at about 180-250oC, 250-400oC and 400-470oC, respectively. The weight loss in the first-stage could be attributed to the reactions of MAA with adjacent MAA or 2-HEMA monomer unit, for which water was lost during the formation of anhydride or ester group. Because the ranges of thermal decompositions for poly(2-HEMA) and poly(BZMA) were 250-430oC and 250-400oC, respectively, the second-stage decomposition in Fig. 3 was due to both 2-HEMA and BZMA segments. This explains why the weight loss of the binder containing 72% BZMA, B72M18H10, in Fig. 3(a) was most obvious of the three samples over the temperature range 250-400oC. For the third-stage decomposition, the weight loss could largely be attributed to the MAA units (the thermal decomposition range of poly(MAA) is 370-470oC) in the binders. Therefore, the third-stage degradation temperature increased as the MAA content increased. For example, Fig. 3(a) demonstrates that the highest third-stage thermal degradation temperature of the three samples was the binder B54M36H10. Fig. 3(b) shows that the extent of the first-stage decomposition increased as the 2-HEMA and MAA content increased; furthermore, the decomposition of the binder “B56M14H30” was most evident over the temperature range of 250-430oC due to its high 2-HEMA content. In addition, Td10 also increased with increasing MAA content in the binder, cf. Table 1.  Table 1 Thermal behaviors of the prepared three-component binders. BZMA/MAA Thermal behaviors Sample (molar ratio) Tg (oC) Td10 (oC) B81M9H10 9:1 74.4 316.8B72M8H20 9:1 74.7 314.8B63M7H30 9:1 74.8 310.8B54M6H40 9:1 73.6 302.5B72M18H10 8:2 87.1 328.8B64M16H20 8:2 86.5 314.4B56M14H30 8:2 86.2 307.9B48M12H40 8:2 85.8 306.6B63M27H10 7:3 99.9 329.7B56M24H20 7:3 99.0 322.9B49M21H30 7:3 93.8 316.8B54M36H10 6:4 120.4 329.8B48M32H20 6:4 110.1 323.5B42M28H30 6:4 109.9 318.6 (a) 0 100 200 300 400 500 60002040608010010% weight lossB72M18H10B63M27H10B54M36H10Temperature (oC)Weight (%)  4(b) 0 100 200 300 400 500 60002040608010010% weight lossB56M14H30B64M16H20B80M20H0Temperature (oC)Weight (%)  Fig. 3 TGA thermograms of the prepared binders. (a) 10 mol% 2-HEMA (b) molar ratio of BZMA/MAA= 4: 1.  (b) Characterization of chemical structure Fig. 4(a) illustrates the FTIR spectrum of a prepared three-component binder, B54M36H10. The absorption peaks at 3500 and 3261cm-1 were due to the –OH stretching bands of hydroxyl group and carboxyl group, respectively. The =C-H stretching band of the aromatic ring (BZMA unit) was observed from 2950 to 3065cm-1, and the C=O stretching band of the carbonyl group at 1729cm-1 (MAA unit) and 1708cm-1 (2-HEMA unit) could also be observed. For the 2-HEMA unit, the stretching band of the ester group (C-O-C) was observed at 1146cm-1. Furthermore, two C-H vibration bands of monosubstituted benzene (BZMA unit) were observed at 701 and 748 cm-1. The spectrum suggests that the three kinds of acrylate monomers were successfully linked together to form a binder by free-radical polymerization. Fig. 4(b) shows FTIR spectrum of the binder, B54M36H10, that had been baked at 220oC for 1h. The asymmetric and symmetric stretching vibrations of the two C=O groups of a formed anhydride were observed at 1805cm-1 and 1762cm-1, respectively; furthermore, the anhydride also had a strong band at 1019cm-1 due to the C-O-C stretching vibration. This result indicates that the anhydride was produced after the binder was baked at 220oC for 1h. Therefore, as the binder contained more MAA or 2-HEMA, the weight loss in the first-stage degradation of TGA experiment would be more pronounced, in accordance with the TGA results shown in Fig. 3.   Fig. 4 FTIR spectra of the three-component binder, B54M36H10. (a) before and (b) after baked at 220oC for 1h.   CONCLUSIONS In this research, three-component binders composed of MAA, BZMA, and 2-HEMA were prepared by means of free radical copolymerization. The thermal behaviors, chemical structures, and other general properties of the formed binders were investigated. Compositions of the monomers for binder synthesis were determined with the aid of a ternary composition diagram. As the MAA content was increased, not only was the acid value but also the thermal stability of the binders, e.g., Tg and Td, enhanced.   5REFERENCES 1. Jeng, R. J.; Chan, L. H.; Lee, R. H.; Hsiue, G. H.; Chang, H. L. J Macromol Sci 2001, 38, 1259. 2. Kubota, S.; Yamawaki, Y.; Moriwaki, T.; Eto, S. Polym Eng Sci 1989, 29, 950.  3. Kubota, S.; Moriwaki, T.; Ando, T.; Fukami, A. J Appl Polym Sci 1987, 33, 1763.  4. Ueda, M.; Nakayama, T. Macromolecules 1996, 29, 6427. 5. Chae, K. H.; Sun, G. J.; Kang, J. K.; Kim, T. H. J Appl Polym Sci 2002, 86, 1172. 6. Nasrullah, J. M.; Dhamodharan, R. J Appl Polym Sci 2004, 92, 1902. 7. Cho, H.; Kim, J.; Patil, P.; Kim, J. Y.; Kim, T. H. J Appl Polym Sci 2007, 103, 3560. 8. Kobayashi, K. Solid State Technol 1992, 11, 15. 9. Sabnis, R. W. Displays 1999, 20, 119.  6 計畫成果自評 (1)研究內容與原計畫相符程度  本研究計畫預定完成之內容有：起始劑及鏈轉移劑於 Binder 的添加量、合成不同配方 Binder、酸價、分子量及黏度之分析、Binder 熱分析及探討、最佳化之 Binder 組成及製程，本研究內容與計畫完全相符。  (2)達成預期目標情況  結合劑於光阻組成中為關鍵的成分之ㄧ，經過二成份及三成份結合劑的合成及性質比較後，再搭配三成分組成座標圖，本研究已成功獲得最佳化三成份結合劑之比例區塊。  (3)研究成果之學術或應用價值  本研究中所製備之三成分組成座標圖可以提供系統化之比較方式，並且獲得最佳添加比例，因而可應用於製備奈米粒子改質負型光阻，進而達成製備彩色光阻之潛力。  (4)是否適合在學術期刊發表或申請專利  本研發成果將發表於國際性期刊，目前已擇定國際期刊進行投稿。  

Preparation of Nano-Silica Modified Negative Acrylate Color Resist

http://tkuir.lib.tku.edu.tw:8080/dspace/bitstream/987654321/6916/1/962221E032032.pdf

[[alternative]]Preparation of Nano-Silica Modified Negative Acrylate Color Resist

Abstract

Similar works

Full text

Available Versions

Tamkang University Institutional Repository