TWI708123B - 光阻劑組成物及使用其製造薄膜電晶體基板之方法 - Google Patents
光阻劑組成物及使用其製造薄膜電晶體基板之方法 Download PDFInfo
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- TWI708123B TWI708123B TW104102383A TW104102383A TWI708123B TW I708123 B TWI708123 B TW I708123B TW 104102383 A TW104102383 A TW 104102383A TW 104102383 A TW104102383 A TW 104102383A TW I708123 B TWI708123 B TW I708123B
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Images
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Abstract
一種光阻劑組成物係包含:相對於100重量份的丙烯醯基共聚物,約0.1至約30重量份的光起始劑,約1至約50重量份的包含至少五個官能基之第一丙烯酸酯單體,約1至約50重量份的包含至多四個官能基之第二丙烯酸酯單體。
Description
實施例係關於一種光阻劑組成物。更具體而言,實施例係關於一種形成用於顯示裝置的絕緣層的光阻劑組成物, 以及利用光阻劑組成物之製造薄膜電晶體基板的方法。
通常,用於顯示裝置的顯示基板包含作為開關元件以用於驅動像素單元的薄膜電晶體、連接至薄膜電晶體的訊號線以及像素電極。訊號線包含提供閘極訊號的閘極線以及與閘極線交叉且提供數據訊號的數據線。
顯示基板可包含用於絕緣電極及絕緣線或用於平坦化基板的有機絕緣層。例如,顯示基板可包含覆蓋薄膜電晶體的有機絕緣層。像素電極可藉由穿過有機絕緣層而形成的接觸孔連接至汲極電極。
實施例係涉及一種光阻劑組成物,其包含:約100重量份的丙烯醯基共聚物、約0.1至約30重量份的光起始劑、約1至約50重量份的包含至少五個官能基之第一丙烯酸酯單體以及約1至約50重量份的包含至多四個官能基之第二丙烯酸酯單體,第二丙烯酸酯單體係為選自於下列化學式1至化學式5表示之化合物之群組的至少一者。 〈化學式1〉
其中,於化學式1中,R1係獨立表示為C2-C10伸烷基(alkylene group)或C2-C10氧伸烷基(oxyalkylene group),以及R2係獨立表示為氫原子或C1-C10烷基(alkyl group), 〈化學式2〉
其中,於化學式2中,R1
係獨立表示為C1-C10伸烷基或C1-C10氧伸烷基或聚氧化烯基(polyoxyalkylene group),R2
係表示為羥甲基(hydroxymethyl group)、C3-C10烷基或C3-C10烷氧基(alkoxy group),以及R3
係獨立表示為氫原子或C1-C10烷基, 〈化學式3〉
其中,於化學式3中,R1
係表示為伸苯基(phenylene group)、三環癸烯基(tricyclodecylene group)、伸金剛烷基(adamantylene group)、伸降冰片烷基(norboranylene group)、雙酚A基(bisphenol-A group)或雙酚F基(bisphenol-F group),以及R2
係獨立表示為氫原子或具有1至10個碳原子的烷基, 〈化學式4〉
其中,於化學式5中,R1
係獨立表示為C1-C10伸烷基或C1-C10氧伸烷基。
光阻劑組成物可進一步包含溶劑,使得光阻劑組成物之固體含量重量為約10至約50%。
丙烯醯基共聚物可經由自由基聚合反應以包含不飽和烯烴化合物(unsaturated olefin compound)及不飽和羧酸(unsaturated carboxylic acid)的共聚合單體所製備而成。
丙烯醯基共聚物之重量平均分子量可為約3000至約30000。
第一丙烯酸酯單體可包含選自於雙季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate )、雙季戊四醇五丙烯酸酯(dipentaerythritol pentaacrylate)、雙季戊四醇羥基五丙烯酸酯(dipentaerythritol hydroxypentaacrylate)、雙季戊四醇烷基醯基五丙烯酸酯(dipentaerythritol alkyloylpentaacrylate)以及己內醯胺取代之雙季戊四醇六丙烯酸酯(caprolactam-substituted dipentaerythritol hexaacrylate)之群組的至少一者。
光起始劑可包含肟酯化合物(oximeester compound)。
光阻劑組成物可進一步包含,相對於約100重量份的丙烯醯基共聚物,重量份為約1至約50的多功能丙烯酸酯寡聚物(multifunctional acrylate oligomer),多功能丙烯酸酯寡聚物係包含選自於脂族胺基甲酸酯丙烯酸酯寡聚物(aliphatic urethane acrylate oligomer)、芳香族胺基甲酸酯丙烯酸酯寡聚物(aromatic urethane acrylate oligomer)、環氧基丙烯酸酯寡聚物(epoxy acrylate oligomer)、環氧基丙烯酸甲酯寡聚物(epoxy methacrylate oligomer)、矽基丙烯酸酯寡聚物(silicon acrylate oligomer)、三聚氰胺丙烯酸酯寡聚物(melamine acrylate oligomer)以及樹枝狀丙烯酸酯寡聚物(dendritic acrylate oligomer)之群組的至少一者。
實施例亦涉及一種形成薄膜電晶體基板之方法,其包含:形成薄膜電晶體在基底基板、塗布光阻劑組成物在薄膜電晶體以形成光阻層,以光束曝光光阻層、以及顯影光阻層。光阻劑組成物可包含:約100重量份的丙烯醯基共聚物、約0.1至約30重量份的光起始劑、約1至約50重量份的包含至少五個官能基的第一丙烯酸酯單體以及約1至約50重量份的包含至多四個官能基的第二丙烯酸酯單體,且包含選自於下列化學式1至化學式5表示之化合物之群組的至少一者: 〈化學式1〉
其中,於化學式2中,R1
係獨立表示為C1-C10伸烷基或C1-C10氧伸烷基或聚氧化烯基,R2
係表示為羥甲基、C3-C10烷基或C3-C10烷氧基,以及R3
係獨立表示為氫原子或C1-C10烷基, 〈化學式3〉
其中,於化學式5中,R1係獨立表示為C1-C10伸烷基或C1-C10氧伸烷基。
光阻劑組成物可進一步包含溶劑,使得光阻劑組成物之固體含量重量為約10至約50%。
丙烯醯基共聚物係可經由自由基聚合反應以包含不飽和烯烴化合物及不飽和羧酸的共聚合單體所製備而成。
丙烯醯基共聚物之重量平均分子量可為約3000至約30000。
第一丙烯酸酯單體可包含選自於雙季戊四醇六丙烯酸酯、雙季戊四醇五丙烯酸酯、雙季戊四醇羥基五丙烯酸酯、雙季戊四醇烷基醯基五丙烯酸酯以及己內醯胺取代之雙季戊四醇六丙烯酸酯之群組的至少一者。
光起始劑可包含肟酯化合物。
光阻劑組成物可進一步包含,相對於約100重量份的丙烯醯基共聚物,重量份為約1至約50的多功能丙烯酸酯寡聚物,多功能丙烯酸酯寡聚物係包含選自於脂族胺基甲酸酯丙烯酸酯寡聚物、芳香族胺基甲酸酯丙烯酸酯寡聚物、環氧基丙烯酸酯寡聚物、環氧基丙烯酸甲酯寡聚物、矽基丙烯酸酯寡聚物、三聚氰胺丙烯酸酯寡聚物以及樹枝狀丙烯酸酯寡聚物之群組的至少一者。
以光束曝光光阻層之前,基底基板可在約80℃至約120℃下預烘烤。
在顯影光阻層之後,基底基板可在約150℃至約250℃下硬化烘烤。
現於下文中,將參照附圖更充分的描述例示性實施例;然而,其可以各種不同形式實施,而不應理解為限制於本文所闡述的實施例。相反的,這些例示性實施例的提供使得本揭露將徹底及完整,且將充分傳達例示性實施方式予此技術領域中具有通常知識者。
在附圖中,為清楚起見可誇大層及區域的尺寸。而應當了解的是,當層或構件被指為「於…上 (on)」其他層或基板時,其可直接於其他層或基板上,或亦可存在中間層。於整篇說明書中,相似的參考符號表示相似的構件。
光阻劑組成物 根據例示性實施例之光阻劑組成物包含丙烯醯基共聚物、光起始劑、包含至少五個官能基的第一丙烯酸酯單體以及具有至多四個官能基的第二丙烯酸酯單體。
例如,光阻劑組成物可包含,相對於100重量份的丙烯醯基共聚物,約0.1至約30重量份的光起始劑、約1至約50重量份的第一丙烯酸酯單體、約1至約50重量份的第二丙烯酸酯單體。光阻劑組成物可進一步包含溶劑,使得光阻劑組成物之固體含量重量為約10至約50%。
丙烯醯基共聚物係可經由自由基聚合反應且在溶劑及聚合反應起始劑的存在下,以包含不飽和烯烴化合物及不飽和羧酸的共聚合單體所製備而成。
不飽和羧酸的範例可包含丙烯酸(acrylic acid)、甲基丙烯酸(methacrylic acid)、丁烯二酸(maleic acid)、反丁烯二酸(fumaric acid)、甲基順丁烯二酸(citraconic acid)、甲基反丁烯二酸(mesaconic acid)、亞甲基丁二酸(itaconic acid)、二羧基無水物(dicarboxyl anhydrates)、或其類似物。這些可單獨使用或以其組合使用。
當基於單體的總重量,不飽和羧酸的含量重量小於約5%時,丙烯醯基共聚物可不溶於鹼性溶液。當基於單體的總重量,不飽和羧酸的含量重量大於約40%時,在鹼性溶液中的丙烯醯基共聚物的可溶性可能過度增加。因此,在形成丙烯醯基共聚物的不飽和羧酸的含量重量,基於單體的總重量,可例如為約5%至約40%。
不飽和烯烴化合物之範例可包含甲基丙烯酸甲酯(methyl methacrylate)、乙基甲基丙烯酸酯(ethyl methacrylate)、甲基丙烯酸正丁酯(N-butyl methacrylate)、甲基丙烯酸仲丁酯(sec-butyl methacrylate)、甲基丙烯酸叔丁酯(tert-butyl methacrylate)、丙烯酸甲酯(methyl acrylate)、丙烯酸異丙酯(isopropyl acrylate)、甲基丙烯酸環己酯(cyclohexyl methacrylate)、2-甲基環己基甲基丙烯酸酯(2-methyl cyclohexyl methacrylate)、丙烯酸二環戊烯酯(dicyclopentenyl acrylate)、丙烯酸雙環戊酯(dicyclopentanyl acrylate)、甲基丙烯酸二環戊烯酯(dicyclopentenyl methacrylate)、甲基丙烯酸二環戊酯(dicyclopentanyl methacrylate)、甲基丙烯酸二環戊氧基乙酯(dicyclopentanyloxyethyl methacrylate)、甲基丙烯酸異莰酯(isobornyl methacrylate)、丙烯酸環己酯(cyclohexyl acrylate)、2-甲基環己基丙烯酸酯(2-methylcyclohexyl acrylate)、丙烯酸二環戊氧基乙酯(dicyclopentanyloxyethyl acrylate)、異冰片基丙烯酸酯(isobornyl acrylate)、甲基丙烯酸苯酯(phenyl methacrylate)、丙烯酸苯酯(phenyl acrylate)、苄基丙烯酸酯(benzyl acrylate)、2-羥乙基甲基丙烯酸酯(2-hydroxyethyl methacrylate)、苯乙烯(styrene)、α-甲基苯乙烯(alpha-methylstyrene)、m-甲基苯乙烯(m-methylstyrene)、p-甲氧基苯乙烯(p-methoxystyrene)、乙烯基甲苯(vinyltoluene)、p-甲基苯乙烯(p-methylstyrene)、1,3-丁二烯(1,3-butadiene)、異戊二烯(isoprene)、2,3-二甲基-13-丁二烯(2,3-dimethyl-1,3-butadien)、丙烯酸縮水甘油酯(acrylic acid glycidyl)、甲基丙烯酸縮水甘油酯(methacrylic acid glycidyl)、α-乙基丙烯酸縮水甘油酯(α-ethyl acrylic acid glycidyl)、α-正丙基丙烯酸縮水甘油酯(α-n-propyl acrylic acid glycidyl)、α-正丁基丙烯酸縮水甘油酯(α-n-butyl acrylic acid glycidyl)、丙烯酸-β-甲基縮水甘油酯(acrylic acid-β-methyl glycidyl)、甲基丙烯酸-β-甲基縮水甘油酯(methacrylic acid-β-methyl glycidyl)、丙烯酸-β-乙基縮水甘油酯(acrylic acid-β-ethyl glycidyl)、甲基丙烯酸-β-乙基縮水甘油酯(methacrylic acid-β-ethyl glycidyl)、丙烯酸-3,4-環氧丁基(acrylic acid-3,4-epoxybutyl)、甲基丙烯酸-3,4-環氧丁基(methacrylic acid-3,4-epoxybutyl)、丙烯酸-6,7-環氧庚基(acrylic acid-6,7-epoxy heptyl)、甲基丙烯酸-6,7-環氧庚基(methacrylic acid-6,7-epoxy heptyl)、α-乙基丙烯酸-6,7-環氧庚基(α-ethyl acrylic acid-6,7-epoxy hepty)l、o-乙烯基芐基縮水甘油醚(o-vinylbenzyl glycidyl ether)、m-乙烯基芐基縮水甘油醚(m-vinyl benzylglycidyl ether)、p-乙烯基芐基縮水甘油醚(p-vinylbenzyl glycidyl ether)、或甲基丙烯酸-3,4-環氧環己基)(methacrylic acid-3,4-epoxycyclohexyl)。這些可單獨使用或以其組合使用。
用於形成丙烯醯基共聚物之溶劑的範例可包含甲醇(methanol)、四氫呋喃(tetrahydrofuran)、甲苯(toluene)、二噁烷(dioxine)、或其類似物。
聚合反應起始劑可包含自由基聚合反應起始劑。聚合反應起始劑的範例可包含2,2'-偶氮雙異丁腈(2,2’-azobisisobutylnitrile)、2,2'-偶氮雙-(2,4-二甲基戊腈)(2,2’-azobis(2,4-dimethylvaleronitrile))、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)(2,2’-azobis(4-methoxy-2,4-dimethylvaleronitrile))、1,1'-偶氮雙-(環己烷-1-碳化睛)(1,1’-azobis(cyclohexane-1-carbonitrile))、二甲基-2,2’-偶氮雙異丁酸酯(dimethyl 2,2’-azobisisobutylate)、或其類似物。
在溶劑及聚合反應起始劑的存在下進行自由基聚合反應之後,未反應的單體可經由沉澱、過濾以及真空乾燥來移除,因而得到丙烯醯基共聚物。丙烯醯基共聚物的換算為聚苯乙烯的重量平均分子量可為約3000至30000。當丙烯醯基共聚物的重量平均分子量小於3000時,可能降低顯影能力、殘餘率以及耐熱性或其類似特性。當丙烯醯基共聚物的重量平均分子量大於30000時,其可能難以形成精細的圖樣。
第一丙烯酸酯單體包含至少五個官能基。第一丙烯酸酯單體之範例可包含雙季戊四醇六丙烯酸酯、雙季戊四醇五丙烯酸酯、雙季戊四醇羥基五丙烯酸酯、雙季戊四醇烷基醯基五丙烯酸酯、己內醯胺取代之雙季戊四醇六丙烯酸酯、或其類似物。這些可單獨使用或以其組合使用。
當第一丙烯酸酯單體的含量相對於約100重量份的丙烯醯基共聚物為小於1重量份時,可能降低其靈敏度,因而降低殘餘率。當第一丙烯酸酯單體的含量相對於約100重量份的丙烯醯基共聚物為大於50重量份時,可能降低顯影能力以及解析度。因此第一丙烯酸酯單體的含量相對於約100重量份的丙烯醯基共聚物可為約1至50重量份,或例如為約10至约30重量份。
第二丙烯酸酯單體包含至多四個官能基。第二丙烯酸酯單體在形成光阻圖樣之製程中可降低煙霧。
於化學式2中,R1
係獨立表示為具有1至10個碳原子的伸烷基、氧伸烷基或聚氧化烯基。R2
係表示為羥甲基、具有3至10個碳原子的烷基或烷氧基。R3
係獨立表示為氫原子或具有1至10個碳原子的烷基。 〈化學式3〉
於化學式3中,R1
係表示為苯甲基(benzyl group)(例如,伸苯基)、三環癸烷基(tricyclodecane group)(例如,三環癸烯基)、降莰烷基(norbornanyl group)(例如,伸降冰片烷基(norbornanylene group))、金剛烷基(adamantly group)(例如,伸金剛烷基(adamantylene group))、雙酚A基或雙酚F基。R2
係獨立表示為氫原子或具有1至10個碳原子的烷基。 〈化學式4〉
於化學式5中,R1
係獨立表示為具有1至10個碳原子的伸烷基或氧伸烷基。
於化學式9中,n係表示為1至3的整數。
當第二丙烯酸酯單體的含量相對於約100重量份的丙烯醯基共聚物為小於1重量份時,可能降低其靈敏度,因而降低殘餘率。當第二丙烯酸酯單體的含量相對於約100重量份的丙烯醯基共聚物為大於50重量份時,可能降低顯影能力以及解析度。因此第二丙烯酸酯單體的含量相對於約100重量份的丙烯醯基共聚物可為約1至50重量份,或例如為約5至20重量份。
溶劑的範例可包含例如,如甲醇以及乙醇的醇類,如四氫呋喃的酯類,如乙二醇單甲醚(ethylene glycol monomethyl ether)以及乙二醇單乙醚(ethylene glycol monoethyl ether)的乙二醇醚類(glycol ethers);如甲基溶纖劑乙酸酯(methyl cellosolve acetate)以及乙基溶纖劑乙酸酯(ethyl cellosolve acetate)的乙二醇烷基醚乙酸酯類(ethylene glycol alkyl ether acetates);如二乙二醇單甲醚(diethylene glycol monomethyl ether)、二乙二醇單乙醚(diethylene glycol monoethyl ether)以及二乙二醇二甲醚(diethylene glycol dimethyl ether)的二乙二醇類(diethylene glycols);如丙二醇甲醚(propylene glycol methyl ether)、丙二醇乙醚(propylene glycol ethyl ether)、丙二醇丙醚(propylene glycol propyl ether)以及丙二醇丁醚(propylene glycol butyl ether)的丙二醇單烷基醚類(propylene glycol monoalkyl ethers);如丙二醇甲醚醋酸酯(propylene glycol methyl ether acetate)、丙二醇乙醚醋酸酯(propylene glycol ethyl ether acetate)、丙二醇丙醚醋酸酯(propylene glycol propyl ether acetate)以及丙二醇丁醚醋酸酯(propylene glycol butyl ether acetate)的丙二醇烷基醚醋酸酯類(propylene glycol alkyl ether acetates);如丙二醇甲醚丙酸酯(propylene glycol methyl ether propionate)、丙二醇乙醚丙酸酯(propylene glycol ethyl ether propionate)、丙二醇丙醚丙酸酯(propylene glycol propyl ether propionate)以及丙二醇丁醚丙酸酯(propylene glycol butyl ether propionate)的丙二醇烷基醚丙酸酯類(propylene glycol alkyl ether propionates);如甲苯以及二甲苯(xylene)的芳香族化合物類;如甲基乙基酮(methyl ethyl ketone)、環己酮(cyclohexanone)以及4-羥基-4-甲基-2-戊酮(4-hydroxy-4-methyl-2-pentanone)的酮類(ketones);以及如乙酸甲酯(methyl acetate)、乙酸乙酯(ethyl acetate)、乙酸丙酯(propyl acetate)、乙酸丁酯(butyl acetate)、2-羥基丙酸乙酯(ethyl 2-hydroxypropionate)、2-羥基異丁酸甲酯(methyl 2-hydroxy-2-methyl propionate)、2-羥基異丁酸乙酯(ethyl 2-hydroxy-2-methyl propionate)、羥基乙酸甲酯(methyl hydroxyacetate)、羥基乙酸乙酯(ethyl hydroxyacetate)、羥基乙酸丁酯(butyl hydroxyacetate)、乳酸甲酯(methyl lactate)、乳酸乙酯(ethyl lactate)、硫酸乳酸丙酯(propyl lactate sulfate)、乳酸丁酯(butyl lactate)、3-羥基丙酸甲酯(methyl 3-hydroxypropionate)、3-羥基丙酸乙酯(ethyl 3-hydroxypropionate)、3-羥基丙酸丙酯(propyl 3-hydroxypropionate)、3-羥基丙酸丁酯(butyl 3-hydroxypropionate)、2-羥基-3-甲基丁酸甲酯(methyl 2-hydroxy-3-methyl butanoate)、甲氧基乙酸甲酯(methyl methoxy acetate)、甲氧基乙酸乙酯(ethyl methoxy acetate)、甲氧基乙酸丙酯(propyl methoxy acetate)、甲氧基乙酸丁酯(butyl methoxy acetate)、乙氧基乙酸甲酯(methyl ethoxy acetate)、乙氧基乙酸乙酯(ethyl ethoxy acetate)、乙氧基乙酸丙酯(propyl ethoxy acetate)、乙氧基乙酸丁酯(butyl ethoxy acetate)、丙氧基乙酸甲酯(methyl propoxy acetate)、丙氧基乙酸乙酯(ethyl propoxy acetate)、丙氧基乙酸丙酯(propyl propoxy acetate)、丙氧基乙酸丁酯(butyl propoxy acetate)、丁氧基乙酸甲酯(methyl butoxy acetate)、丁氧基乙酸乙酯(ethyl butoxy acetate)、丁氧基乙酸丙酯(propyl butoxy acetate)、丁氧基乙酸丁酯(butyl butoxy acetate)、2-甲氧基丙酸甲酯(methyl 2-methoxypropionate)、2-甲氧基丙酸乙酯(ethyl 2-methoxypropionate)、2-甲氧基丙酸丙酯(propyl 2-methoxypropionate)、2-甲氧基丙酸丁酯(butyl 2-methoxypropionate)、2-乙氧基丙酸甲酯(methyl 2-ethoxypropionate)、2-乙氧基丙酸乙酯(ethyl 2-ethoxypropionate)、2-乙氧基丙酸丙酯(propyl 2-ethoxypropionate)、2-乙氧基丙酸丁酯(butyl 2- ethoxypropionate)、2-丁氧基丙酸甲酯(methyl 2-butoxypropionate)、2-丁氧基丙酸乙酯(ethyl 2-butoxypropionate)、2-丁氧基丙酸丙酯(propyl 2-butoxypropionate)、2-丁氧基丙酸丁酯(butyl 2-butoxypropionate)、3-甲氧基丙酸甲酯(methyl 3-methoxypropionate)、3-甲氧基丙酸乙酯(ethyl 3-methoxypropionate)、3-甲氧基丙酸丙酯(propyl 3-methoxypropionate)、3-甲氧基丙酸丁酯(butyl 3-methoxypropionate)、3-乙氧基丙酸甲酯(methyl 3-ethoxypropionate)、3-乙氧基丙酸乙酯(ethyl 3-ethoxypropionate)、3-乙氧基丙酸丙酯(propyl 3-ethoxypropionate)、3-乙氧基丙酸丁酯(butyl 3-ethoxypropionate)、3-丙氧基丙酸甲酯(methyl 3-propoxypropionate)、3-丙氧基丙酸乙酯(ethyl 3-propoxypropionate)、3-丙氧基丙酸丙酯(propyl 3-propoxypropionate)、3-丙氧基丙酸丁酯(butyl 3-propoxypropionate)、3-丁氧基丙酸甲酯(methyl 3-butoxypropionate)、3-丁氧基丙酸乙酯(ethyl 3-butoxypropionate)、3-丁氧基丙酸丙酯(propyl 3-butoxypropionate)、3-丁氧基丙酸丁酯(butyl 3-butoxypropionate)的酯化合物類(ester compounds),或其類似物。這些可單獨使用或以其組合使用。上述範例之中,在考慮構成光阻劑組成物的各組成成分的溶解度及反應性下可使用乙二醇醚類、乙二醇烷基醚乙酸酯類以及二乙二醇類。
例如,基於光阻劑組成物的總重量,溶劑可被添加,使得光阻劑組成物的固體含量約為10至50%重量比,或例如重量約15至40%重量比。
光阻劑組成物可進一步包含多功能丙烯酸酯寡聚物。例如,多功能丙烯酸酯寡聚物的含量相對於約100重量份的丙烯醯基共聚物可為約1至50重量份。多功能丙烯酸酯寡聚物可具有2至20個官能基。
多功能丙烯酸酯寡聚物的範例可包含脂族胺基甲酸酯丙烯酸酯寡聚物、芳香族胺基甲酸酯丙烯酸酯寡聚物、環氧基丙烯酸酯寡聚物、環氧基丙烯酸甲酯寡聚物、矽基丙烯酸酯寡聚物、三聚氰胺丙烯酸酯寡聚物、樹枝狀丙烯酸酯寡聚物、或其類似物。這些可單獨使用或以其組合使用。
光阻劑組成物可進一步包含如三聚氰胺交聯劑、矽烷耦合劑、或其類似物的黏著促進劑。黏著促進劑相對於約100重量份的丙烯醯基共聚物可為1至10重量份。
矽烷耦合劑的範例可包含KBM-303、KBM-403、KBE-402、KBE-40(商品名,Shitetsu,日本)、或其類似物。三聚氰胺交聯劑的範例可包含MW-30M、MX-706(商品名,VISIONTECH,韓國)、或其類似物。這些可單獨使用或以其組合使用。
根據例示性實施例之光阻劑組成物可被塗布、預烘烤、曝光、顯影以及硬化烘烤以形成光阻圖樣。可減少如在預烘烤製程或硬化烘烤製程的加熱製程中所造成的煙霧或釋出氣體。因此,可減少及/或預防因煙霧或釋出氣體所產生的雜質而造成的故障。
當光阻劑組成物被用於形成顯示面板的有機絕緣層時,可減少接觸孔的殘餘物,且可降低在固化封閉劑的製程中由UV或靠近UV所造成的偏綠效果。
光阻劑組成物可改善光阻圖樣的黏著強度,且可形成具有高穿透性的光阻層。
下文將參照附圖而更充分地描述根據例示性實施例之製造薄膜電晶體基板之方法。
第1圖至第6圖係描述根據例示性實施例之製造薄膜電晶體基板之方法之階段之截面圖。
參照第1圖,包含閘極電極GE之閘極金屬圖樣可形成在基底基板100上。閘極金屬圖樣可進一步包含連接至閘極電極GE的閘極線。
例如,閘極金屬層可形成在基底基板100上,且被圖樣化以形成閘極線及閘極電極GE。基底基板100的範例可包含玻璃基板、石英基板、矽基板、塑膠基板、或其類似物。
可用於閘極金屬層的範例材料可包含銅、銀、鉻、鉬、鋁、鈦、錳、或其合金。閘極金屬層可具有單層結構或可具有包含不同材料的多層結構。例如,閘極金屬層可包含設置在銅層之上及/或之下的銅層及鈦層。
閘極絕緣層110可形成以覆蓋閘極線以及閘極電極GE。閘極絕緣層110可包含矽氮化物、矽氧化物或類似物。閘極絕緣層110可具有單層結構或多層結構。例如,閘極絕緣層110可包含含有矽氮化物的下絕緣層以及含有矽氧化物的上絕緣層。
參照第2圖,半導體層120、歐姆接觸層130以及源極金屬層140可依序形成在閘極絕緣層110上。
半導體層120可包含非晶矽。歐姆接觸層130可包含植入高濃度的n+雜質的非晶矽。在另一個實施方式中,半導體層120可包含氧化半導體。當半導體層120包含氧化半導體時,可省略歐姆接觸層130。
可用於源極金屬層140的範例材料可包含銅、銀、鉻、鉬、鋁、鈦、錳、或其合金。源極金屬層140可具有單層結構或可具有包含不同材料的多層結構。例如,源極金屬層140可具有鉬/鋁/鉬的三層結構。在另一個實施方式中,源極金屬層140可具有包含金屬層以及包含透明導電氧化物的阻絕層的多層結構。
參照第3圖,光阻圖樣可形成在源極金屬層140上。源極金屬層140、歐姆接觸層130以及半導體層120可被圖樣化以形成主動圖樣AP、歐姆接觸圖樣、源極電極SE以及汲極電極DE。
主動圖樣AP可與閘極電極GE重疊。歐姆接觸圖樣可設置在主動圖樣AP上,且可包含接觸源極電極SE的第一歐姆接觸圖樣132以及接觸汲極電極 DE的第二歐姆接觸圖樣134。
閘極電極GE、主動圖樣AP、源極電極SE、以及汲極電極 DE可構成薄膜電晶體。
藉由利用相同遮罩以及利用經由半色調曝光所形成具有梯度厚度的光阻圖樣的相同光刻製程可圖樣化源極金屬層140、歐姆接觸層130、以及半導體層120。
參照第4圖,保護層150可形成在薄膜電晶體上。保護層150可包含如矽氧化物、矽氮化物或類似物的無機絕緣材料。光阻劑組成物可塗布在保護層150上以形成光阻膜160(亦即,光阻層)。光阻劑組成物可包含丙烯醯基共聚物、光起始劑、包含至少五個官能基的第一丙烯酸酯單體以及具有至多四個官能基的第二丙烯酸酯單體。例如,光阻劑組成物可包含,相對於約100重量份的丙烯醯基共聚物,約0.1至約30重量份的光起始劑、約1至約50重量份的第一丙烯酸酯單體、約1至約50重量份的第二丙烯酸酯單體。光阻劑組成物可進一步包含溶劑,使得光阻劑組成物之固體含量重量為約10至約50%。
光阻劑組成物可與根據先前描述的例示性實施例之光阻劑組成物為實質上相同。因此,將不重複任何重複的描述。
光阻劑組成物可塗布在基底基板100上,例如經由旋轉塗布或其類似技術。
光阻膜160可被預烘烤以移除溶劑。例如,光阻膜160可在約80℃至約120℃下加熱。
此後,光阻膜160可經由遮罩200以光束曝光。可利用如UV、電子光束、X 光、或類似物的光束。
遮罩200可設置在光阻膜160上。遮罩200可包含透光部210以及遮光部220。與透光部210重疊之部分的光阻膜160可以光束曝光並硬化。與遮光部220重疊之部分的光阻膜160可不曝露於光束。遮光部220可與汲極電極DE重疊。
參照第5圖,顯影液係提供給光阻膜160。顯影液可為鹼性溶液。可維持與透光部210重疊的部分的光阻膜160以形成有機絕緣層,且可移除與遮光部220重疊的部分的光阻膜160,以形成穿過有機絕緣層的接觸孔CH。因此,經由接觸孔CH可部分地露出保護層150。
顯影液可包含如氫氧化鈉(sodium hydroxide)、氫氧化鉀(potassium hydroxide)或碳酸鈉(sodium carbonate)的無機鹼,如n-丙基胺(n-propyl amine)的一級胺,如二乙胺(diethyl amine)的二級胺,如三甲基胺(trimethyl amine)、甲基二乙胺(methyldiethyl amine)、二甲基乙胺(dimethylethyl amine)或三乙胺(triethyl amine)的三級胺,如二甲基乙醇胺(dimethylethanol amine)、甲基二乙醇胺(methyldiethanol amine)或三乙醇胺(triethanol amine)的醇胺類(alcohol amine),或是如氫氧化四甲基銨(tetramethylammonium hydroxide)或氫氧化四乙基銨(tetraethylammonium hydroxide)的四級銨鹽類(fourth degree ammonium salt)作為示例。
顯影光阻膜160之後,為了改善光阻膜160的黏著強度,可在加熱設備,如烤箱,執行硬化烘烤製程。例如,光阻膜160可在約150℃至250℃下加熱。在執行硬化烘烤製程之前,光阻膜160可進一步以光束曝光,使光阻膜160可進一步固化。下文中,如上所述已處理的光阻膜160將被稱為「有機絕緣層160’」
露出的部分保護層150可被移除以露出部分的汲極電極DE。
參照第6圖,導電層可形成在有機絕緣層160’上且被圖樣化以形成像素電極PE。像素電極PE可包含導電性金屬氧化物、銦錫氧化物、銦鋅氧化物或類似物。
像素電極PE可經由穿過有機絕緣層160’及保護層150的接觸孔CH電性連接至汲極電極DE。
薄膜電晶體基板可藉由封閉劑耦接至相對基板。薄膜電晶體基板可用於液晶顯示面板或有機電致發光顯示面板的顯示基板。
在實施例中,光阻劑組成物可用於形成薄膜電晶體基板的平坦化層。在另一實施例中,光阻劑組成物可用於形成薄膜電晶體基板的各種絕緣層、相對基板的平坦化層、柱間隔件、外敷層、彩色光阻、分隔層或類似物。此外,光阻劑組成物可用於液晶顯示裝置、有機電致發光顯示裝置、電潤濕顯示裝置、電泳顯示裝置、或類似物的製造。
下列提供範例及比較例以強調一或多個實施例的特徵,但應理解的是,範例及比較例不應被解釋為限制實施例之範疇,或是比較例也不應被解釋為在實施例之範疇之外。進一步而言,應理解的是,實施例不應被限制在範例及比較例中所描述的特定細節。 合成範例
約400重量份的四氫呋喃、約30重量份的甲基丙烯酸、約30重量份的苯乙烯(styrene)以及約40重量份的甲基丙烯酸缩水甘油酯(glycidylmethacrylate)放入具有冷卻器及攪拌器且以約600rpm速度混合的燒瓶中。之後,將約15重量份的2,2'-偶氮雙-(2,4-二甲基戊腈)加入於此。將混合物逐漸加熱至約55℃並維持約24小時。之後,將混合物快速地冷卻至室溫。將約500ppm的羥基二苯基甲酮(hydroxybenzophenone)作為聚合反應抑制劑加入至混合物,以得到具有固體含量重量約30%的共聚組成物。
為了移除未反應的單體,相對於約100重量份的共聚組成物,加入約1000重量份的n-己烷用於沉澱。包含未反應單體的不良溶劑利用篩子經由過濾製程自共聚組成物移除。之後,在約55℃或小於55℃下真空乾燥共聚組成物以完全移除殘留溶劑及未反應單體,以得到丙烯醯基共聚物。
如藉由凝膠滲透層析法(GPC)測定,丙烯醯基共聚物的換算為聚苯乙烯的重量平均分子量為約6000。 範例1
將約100重量份的合成範例的丙烯醯基共聚物、約20重量份的下列化學式13表示之光起始劑、約20重量份的雙季戊四醇五丙烯酸酯作為包含至少5個官能基的第一丙烯酸酯單體、約10重量份的下列化學式14表示之第二丙烯酸酯單體混合。加入丙二醇乙醚醋酸酯(Propylene glycol monoethyl acetate)於混合物,使固體含量重量為約20%,且藉由0.2µm的微孔過濾器過濾混合物以製備負型光阻劑組成物。 〈化學式13〉〈化學式14〉範例2
範例1至5以及比較例1至4之負型光阻劑組成物的特性係如下列進行評價,且得到的結果係由下列表1所示。
A)靈敏度:負型光阻劑組成物係藉由旋轉塗布方式塗布在具有矽氮化物層的玻璃基板上,且在加熱板上以約100℃預烘烤約2分鐘,以形成具有約3.4µm厚度的光阻膜。
在約365nm且具有約10mW/cm2
強度的UV光係經由具有自寬帶曝光的預定圖樣的圖樣遮罩以約1至5秒具約0.2秒的間隔照射光阻膜。之後,光阻膜係藉由包含重量約2.50%的氫氧化四甲基銨的水溶液在23℃下顯影約50秒。光阻膜係利用純水清洗約60秒以形成光阻圖樣。
光阻圖樣係在烤箱中以約220℃加熱約60分鐘用於固化。當殘餘率相對於20µm的線以及空間臨界尺寸 (CD)為飽和時,測定靈敏度。
B)最大解析度:測定已形成光阻圖樣的接觸孔之最小尺寸,其能維持在相同的CD偏位,用於評估靈敏度。
C)接觸孔中的浮渣(Scum):測定所形成之光阻圖樣之接觸孔中的浮渣,用於評估靈敏度。「○」表示為沒有浮渣,且「X」表示為觀察到浮渣。
D)黏著強度:測定已形成的光阻圖樣的最小殘餘以用於評估靈敏度。「○」表示為厚度小於約1.0µm、「∆」表示為厚度約1.0µm至約1.5µm,且「X」表示為厚度大於約1.5µm。
E)穿透性:光阻圖樣經由上述相同方法形成在玻璃基板上。藉由分光光度計測定光阻圖樣的穿透性。「○」表示為穿透性大於約93%、「∆」表示為約90%至約93%的穿透性,且「X」表示為穿透性小於約90%。
F) 偏綠效果:用於評估穿透性所形成的光阻圖樣係進一步曝光於來自鐵金屬鹵化物燈之光束,鐵金屬鹵化物燈產生在約200nm至約450nm的光束,相對於約365nm的光束具有約10 J/cm2
的強度。之後,在以光束曝光之前與之後,測定光阻圖樣的顏色座標。「○」表示為顏色座標差小於約10%、「∆」表示為約10%至30%的顏色座標差,且「X」表示為顏色座標差大於約30%。
G)對比比率:用於評估穿透性所使用的基板插入在正常的白色模式的偏光板之間,且藉由對比測試器(型號名稱:CT-1)測定在白色模式的亮度至在黑色模式的亮度的對比比率。「○」表示為對比比率大於約22000、「∆」表示為約20000至約22000的對比比率以及「X」表示為對比比率小於約20000。
H)煙霧量:分別將範例1至5以及比較例1至4的負型光阻劑組成物塗布在玻璃基板上。光阻劑組成物在沖洗及捕集設備中以約100℃預烘烤5分鐘所產生的煙霧係藉由收集管收集。收集的煙霧係藉由定量分析及定性分析分離。「○」表示為煙霧量比率相對於比較例1的煙霧量小於重量的約50%,以及「X」表示為煙霧量比率相對於比較例1的煙霧量未小於重量的約50%。
參照表1,範例1至5的光阻劑組成物在形成光阻圖樣的製程中,可降低煙霧的產生,且可改善光阻圖樣的黏著強度。此外,光阻劑組成物在關於最大解析度、穿透性、偏綠效果以及對比比率上可具有期望的特性。此外,光阻劑組成物可降低或避免光阻圖樣的接觸孔中的浮渣。
因此,可注意到的是,根據範例的光阻劑組成物可增加光刻製程的可靠性,且可適當地用於製造具有高解析度及窄邊框的顯示裝置。
藉由總結與回顧的方式,為了形成有機絕緣層,如覆蓋薄膜電晶體的有機絕緣層,可利用光阻劑組成物。例如,光阻劑組成物可經由塗布、預烘烤、以光束曝光、顯影以及硬化烘烤,以形成具有接觸孔的有機絕緣層。
一般的光阻劑組成物,在如預烘烤製程、硬化烘烤製程或類似製程的加熱製程中可能產生煙霧。煙霧可能在基板上產生雜質,因而汙染腔室或引發缺陷。此外,殘餘物可能剩餘在形成在有機絕緣層的接觸孔中,且有機絕緣層可能會在固化用於結合基板的封閉劑的製程中,由於UV或靠近UV而褪色。
例示性實施例所提供的光阻劑組成物在高溫製程中能夠減少煙霧。
根據實施例,可降低在如預烘烤製程或硬化烘烤製程的加熱製程中所造成的煙霧或釋出氣體。因此,可減少及/或預防因煙霧或釋出氣體所產生的雜質而造成的故障。
根據實施例,當光阻劑組成物係用於形成顯示面板的有機絕緣層時,可減少接觸孔中的殘餘物,且可降低在固化封閉劑的製程中由UV或靠近UV所造成的偏綠效果。
根據實施例,光阻劑組成物可改善光阻圖樣的黏著強度,且可形成具有高穿透性的光阻層。
例示性實施例進一步提供利用光阻劑組成物來製造薄膜電晶體基板之方法。
例示性實施例已於文中揭露,且儘管使用了特定的術語,其僅以一般且描述性的意義使用及解釋,而非用於限制之目的。此外,領域內具通常知識者將理解的是,在未脫離如以下申請專利範圍所述之本發明之精神與範疇下,可進行各種細節與形式上之變更。
100‧‧‧基底基板
110‧‧‧閘極絕緣層
120‧‧‧半導體層
130‧‧‧歐姆接觸層
132‧‧‧第一歐姆接觸圖樣
134‧‧‧第二歐姆接觸圖樣
140‧‧‧源極金屬層
150‧‧‧保護層
160‧‧‧光阻膜
160’‧‧‧有機絕緣層
200‧‧‧遮罩
210‧‧‧透光部
220‧‧‧遮光部
AP‧‧‧主動圖樣
CH‧‧‧接觸孔
DE‧‧‧汲極電極
GE‧‧‧閘極電極
PE‧‧‧像素電極
SE‧‧‧源極電極
對於所屬領域具有通常知識者而言,藉由詳細描述例示性實施例時一併參照附圖將使特點變得顯而易知,其中:
第1至6圖係描述根據例示性實施例之製造薄膜電晶體基板之方法之階段之截面圖。
100‧‧‧基底基板
110‧‧‧閘極絕緣層
132‧‧‧第一歐姆接觸圖樣
134‧‧‧第二歐姆接觸圖樣
150‧‧‧保護層
160’‧‧‧有機絕緣層
AP‧‧‧主動圖樣
DE‧‧‧汲極電極
GE‧‧‧閘極電極
PE‧‧‧像素電極
SE‧‧‧源極電極
Claims (20)
- 一種光阻劑組成物,其包含:一丙烯醯基共聚物,係為約100重量份;一光起始劑,係為約0.1至約30重量份;一第一丙烯酸酯單體,其包含至少五個官能基,係為約1至約50重量份;以及一第二丙烯酸酯單體,其包含至多四個官能基,係為約5至約20重量份,該第二丙烯酸酯單體係為選自於下列化學式1至化學式5表示之化合物之群組的至少一者:
- 如申請專利範圍第1項所述之光阻劑組成物,其進一步包含一溶劑,使得該光阻劑組成物之固體含量重量為約10至約50%。
- 如申請專利範圍第1項所述之光阻劑組成物,其中該丙烯醯基共聚物係經由一自由基聚合反應以包含不飽和烯烴化合物及不飽和羧酸的共聚合單體所製備而成。
- 如申請專利範圍第3項所述之光阻劑組成物,其中該丙烯醯基共聚物之重量平均分子量為約3000至約30000。
- 如申請專利範圍第1項所述之光阻劑組成物,其中該第一丙烯酸酯單體係包含選自於雙季戊四醇六丙烯酸酯、雙季戊四醇五丙烯酸酯、雙季戊四醇羥基五丙烯酸酯、雙季戊四醇烷基醯基五丙烯酸酯以及己內醯胺取代之雙季戊四醇六丙烯酸酯之群組的至少一者。
- 如申請專利範圍第1項所述之光阻劑組成物,其中該光起始劑包含肟酯化合物。
- 如申請專利範圍第1項所述之光阻劑組成物,其進一步包含,相對於100重量份的該丙烯醯基共聚物,重量份為約1至約50的一多功能丙烯酸酯寡聚物,該多功能丙烯酸酯寡聚物係包含選自於脂族胺基甲酸酯丙烯酸酯寡聚物、芳香族胺基甲酸酯丙烯酸酯寡聚物、環氧基丙烯酸酯寡聚物、環氧基丙烯酸甲酯寡 聚物、矽基丙烯酸酯寡聚物、三聚氰胺丙烯酸酯寡聚物以及樹枝狀丙烯酸酯寡聚物之群組的至少一者。
- 一種形成薄膜電晶體基板之方法,該方法包含:形成一薄膜電晶體在一基底基板上;塗布一光阻劑組成物在該薄膜電晶體上以形成一光阻層;以光束曝光該光阻層;以及顯影該光阻層;其中,該光阻劑組成物包含:約100重量份的一丙烯醯基共聚物;約0.1至約30重量份的一光起始劑;約1至約50重量份的包含至少五個官能基的一第一丙烯酸酯單體;以及約5至約20重量份的包含至多四個官能基的一第二丙烯酸酯單體,且包含選自於下列化學式1至化學式5表示之化合物之群組的至少一者:
- 如申請專利範圍第10項所述之方法,其中該光阻劑組成物進一步包含一溶劑,使得該光阻劑組成物之固體含量重量為約10至約50%。
- 如申請專利範圍第10項所述之方法,其中該丙烯醯基共聚物係經由一自由基聚合反應以包含不飽和烯烴化合物及不飽和羧酸的共聚合單體所製備而成。
- 如申請專利範圍第12項所述之方法,其中該丙烯醯基共聚 物之重量平均分子量為約3000至約30000。
- 如申請專利範圍第10項所述之方法,其中該第一丙烯酸酯單體係包含選自於雙季戊四醇六丙烯酸酯、雙季戊四醇五丙烯酸酯、雙季戊四醇羥基五丙烯酸酯、雙季戊四醇烷基醯基五丙烯酸酯以及己內醯胺取代之雙季戊四醇六丙烯酸酯之群組的至少一者。
- 如申請專利範圍第10項所述之方法,其中該光起始劑包含肟酯化合物。
- 如申請專利範圍第10項所述之方法,其中該光阻劑組成物進一步包含,相對於100重量份的該丙烯醯基共聚物,重量份為約1至約50的一多功能丙烯酸酯寡聚物,該多功能丙烯酸酯寡聚物係包含選自於脂族胺基甲酸酯丙烯酸酯寡聚物、芳香族胺基甲酸酯丙烯酸酯寡聚物、環氧基丙烯酸酯寡聚物、環氧基丙烯酸甲酯寡聚物、矽基丙烯酸酯寡聚物、三聚氰胺丙烯酸酯寡聚物以及樹枝狀丙烯酸酯寡聚物之群組的至少一者。
- 如申請專利範圍第10項所述之方法,其中以光束曝光該光阻層之前,該基底基板係在約80℃至約120℃下預烘烤。
- 如申請專利範圍第10項所述之方法,其中在顯影該光阻層之後,該基底基板係在約150℃至約250℃下硬化烘烤。
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