TWI840326B - 間隔壁用圖案的形成方法 - Google Patents
間隔壁用圖案的形成方法 Download PDFInfo
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- TWI840326B TWI840326B TW107104273A TW107104273A TWI840326B TW I840326 B TWI840326 B TW I840326B TW 107104273 A TW107104273 A TW 107104273A TW 107104273 A TW107104273 A TW 107104273A TW I840326 B TWI840326 B TW I840326B
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- resist
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- partition wall
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- CYFIHPJVHCCGTF-UHFFFAOYSA-N prop-2-enyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OCC=C CYFIHPJVHCCGTF-UHFFFAOYSA-N 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- HPCIWDZYMSZAEZ-UHFFFAOYSA-N prop-2-enyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC=C HPCIWDZYMSZAEZ-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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Abstract
本發明係關於一種次像素的至少一部份中嵌入有色別發光體之顯示元件之間隔壁用圖案的形成方法,其係具有於透明基板上圖案化黑色阻劑之步驟(A),及將具有熱硬化能之正型阻劑組成物塗佈於前述黑色阻劑經圖案化之前述透明基板上,形成阻劑膜之步驟(B),及將前述阻劑膜由前述透明基板側進行曝光之步驟(C),及將前述曝光後之阻劑膜進行顯影,並形成阻劑圖案之步驟(D)。
Description
本發明係關於次像素的至少一部份中嵌入有色別發光體之顯示元件之間隔壁用圖案的形成方法。 本申請係基於2017年2月15日於美國申請之美國臨時申請案第62/459,066號而主張優先權,且該內容援用於此。
液晶顯示器等的顯示元件係於相互為對向之2枚基板之間夾著液晶層之構造。然後於其中之一基板的內側中,形成具有由紅色(R)、綠色(G)、藍色(B)等各色所構成之畫素(像素)之色彩濾波器。顯示元件中通常為了使圖像的明暗對比顯著,而形成區劃R、G、B各色的畫素(次像素)之黑色矩陣。
一般而言,色彩濾波器係藉由微影法來形成。具體而言,首先係於基板塗佈、曝光、顯影黑色的感光性組成物,並形成黑色矩陣及間隔壁。之後,接著,將每個R、G、B各色之感光性組成物藉由重複塗佈、曝光、顯影來將各色的圖案形成於特定的位置,來製造色彩濾波器。
專利文獻1中,揭示於有機EL顯示器的次像素間設置遮光壁之方法。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2004-335224號公報
[發明所欲解決的課題]
如同專利文獻1之方法中,由於於黑色矩陣上配置遮光壁,故將產生與黑色矩陣圖案之對準精度的問題。 為了解決與黑色矩陣圖案之對準精度的問題,故亦想到使遮光壁自身亦兼為黑色矩陣之構成。然而,作為這樣構成的情況,若遮光壁變高,則對紫外線之透明性亦變得低下。因此,當黑色矩陣圖案形成時,將產生微影技術變得不適用的問題。 本發明係鑑於上述情況而完成者,其目的在於提供一種於次像素的至少一部份中嵌入有色別發光體之顯示元件中,可形成與黑色矩陣圖案之對準精度良好之間隔壁之間隔壁用圖案的形成方法。 [用以解決課題之手段]
本發明之一態樣為一種間隔壁用圖案的形成方法,其係次像素的至少一部份中嵌入有色別發光體之顯示元件之間隔壁用圖案的形成方法,具有於透明基板上圖案化黑色阻劑之步驟(A),及將具有熱硬化能之正型阻劑組成物塗佈於前述黑色阻劑經圖案化之前述透明基板上,形成阻劑膜之步驟(B),及將前述阻劑膜由前述透明基板側進行曝光之步驟(C),及將前述曝光後之阻劑膜進行顯影,並形成阻劑圖案之步驟(D)。 [發明之效果]
依據本發明,係可提供一種於次像素的至少一部份中嵌入有色別發光體之顯示元件中,可形成與黑色矩陣圖案之對準精度良好之間隔壁之間隔壁用圖案的形成方法。
本說明書及本發明之申請專利範圍中,所謂「脂肪族」係相對於芳香族而言為相反的概念,係定義為不具有芳香族性之基團、化合物等的意思。 「烷基」,若無特別指明,則為包含直鏈狀、分支鏈狀及環狀之1價之飽和烴基者。烷氧基中的烷基亦相同。 「伸烷基」,若無特別指明,則為包含直鏈狀、分支鏈狀及環狀之2價之飽和烴基者。 「鹵化烷基」,為烷基之氫原子的一部份或全部被鹵素原子所取代之基,作為該鹵素原子,可列舉出氟原子、氯原子、溴原子、碘原子。 所謂「構成單元」,係指構成高分子化合物(樹脂、聚合體、共聚物)之單體單元(單體單元)之意。 記載為「可具有置換基」之情況,係包含將氫原子 (-H)以1價之基置換之情況及將亞甲基(-CH2
-)以2價之基置換的情況之兩者。 「曝光」為包含放射線的照射之全部概念。 「(甲基)丙烯酸酯」係為丙烯酸酯及甲基丙烯酸酯之任一者或兩者之意。
以下,係針對本發明的各態樣之實施形態進行詳細說明,然而本發明係並非受到以下實施形態的任何限定者,於本發明的目的之範圍內,可添加適當變更後實施。
[間隔壁用圖案的形成方法] 本實施形態之間隔壁用圖案的形成方法,其係次像素的至少一部份中嵌入有色別發光體之顯示元件之間隔壁用圖案的形成方法,具有於透明基板上圖案化黑色阻劑之步驟(A),及將具有熱硬化能之正型阻劑組成物塗佈於前述黑色阻劑經圖案化之前述透明基板上,形成阻劑膜之步驟(B),及將前述阻劑膜由前述透明基板側進行曝光之步驟(C),及將前述曝光後之阻劑膜進行顯影,並形成阻劑圖案之步驟(D)。 作為色別發光體,係可列舉出化合物螢光體、量子點螢光體等,以往顯示元件之色彩濾波器等中所使用者。其中,由各色之螢光的發光域之狹窄化或使紅色(R)的純度高之觀點來看,較佳係以量子點螢光體作為色別發光體。
<步驟(A)> 步驟(A)中,於透明基板1上將黑色阻劑圖案化(圖1(a)~(c))。 將黑色阻劑圖案化之方法並無特別限制,可使用以往公知的方法。例如,將黑色阻劑於透明基板上使用輥塗佈機、逆轉塗佈機、棒塗佈機等的接觸轉印型塗佈裝置或旋轉器(旋轉式塗佈裝置)、淋幕式平面塗裝機等的非接觸型塗佈裝置來進行塗佈。 接著,使經塗佈之黑色阻劑乾燥後,形成塗膜2。乾燥方法並無特別限制,例如,(1)藉由加熱板於80℃至120℃,較佳係90℃至100℃之溫度下,乾燥60秒鐘至120秒鐘之方法,(2)於室溫下放置數小時至數日之方法,(3)放入暖風加熱器或紅外線加熱器中數十分鐘至數小時將溶劑去除之方法,之中之任一方法皆可使用。 接著,於此塗膜2上,介隔遮罩照射紫外線、準分子雷射光等的活性能量射線,進行部分曝光。所照射之能量射線量雖係因黑色阻劑的組成而有所不同,然而較佳係為例如30mJ/cm2
至2000mJ/cm2
之程度。 接著,藉由將曝光後的膜藉由顯影液來顯影,圖案化為所期望的形狀。顯影方法並無特別限制,可使用例如浸漬法、噴塗法等。作為顯影液,可列舉出乙醇胺、二乙醇胺、三乙醇胺等的有機系的顯影液,或氫氧化鈉、氫氧化鉀、碳酸鈉、氨、4級銨鹽等的水溶液。 接著,將顯影後的圖案以200~250℃之程度進行後烘烤。 藉由以上,可於透明基板上將黑色阻劑以特定的形狀進行圖案化。 透明基板上經圖案化之黑色阻劑(黑色矩陣2a)的厚度一般係可設定為0.5μm~5μm之範圍內,較佳為1μm~3μm,更佳為1μm~2μm。 特別是,由提高黑色矩陣圖案的解析性之觀點來看,黑色矩陣的厚度較佳為3μm以下。
(透明基板) 作為透明基板,若為具有透光性之基板則無特別限制,然而可使用一般玻璃基板。
(黑色阻劑) 作為黑色阻劑並無特別限制,可使用以往公知者。例如,可舉出含有黑色顏料及樹脂成分之感光性樹脂組成物等。 作為黑色顏料,可列舉出碳黑、鈦黑、銅、鐵、錳、鈷、鉻、鎳、鋅、鈣、銀等的金屬氧化物、複合氧化物、金屬硫化物、金屬硫酸鉛或金屬碳酸鹽等的無機顏料等。此等的黑色顏料之中,更佳為使用具有高遮光性之碳黑或鈦黑。 作為碳黑,可使用槽黑、爐黑、熱裂碳黑、燈黑等公知的碳黑。又,為提升在黑色組成物中的分散性,更佳係使用樹脂塗層碳黑。 作為樹脂成分,可列舉出環氧樹脂、丙烯酸環氧樹脂、丙烯酸樹脂、矽氧烷聚合物系樹脂、聚醯亞胺樹脂、含矽聚醯亞胺樹脂、聚醯亞胺矽氧烷樹脂、馬來醯亞胺樹脂等的聚醯亞胺系樹脂。
黑色阻劑可為正型感光性組成物,亦可為負型感光性組成物。 黑色阻劑為正型之情況,黑色阻劑較佳係含有鹼可溶性樹脂、感光劑及黑色顏料。 黑色阻劑為負型感光性樹脂組成物之情況,黑色阻劑較佳係含有光聚合性化合物、光聚合起始劑及黑色顏料。
<步驟(B)> 步驟(B)中,將具有熱硬化能之正型阻劑組成物塗佈於前述黑色阻劑經圖案化之前述透明基板上,形成阻劑膜3(圖1(d))。 例如,將具有熱硬化能之正型阻劑組成物以旋轉器、旋轉塗佈機、輥塗佈機、噴塗機、縫塗佈機等來塗佈,並使其乾燥而形成阻劑膜。 作為上述乾燥的方法,係可舉例為例如,藉由加熱板以80~120℃之溫度乾燥120~500秒之方法。 上述阻劑膜3的膜厚係無特別限制者,然而較佳為6μm~50μm,更佳為6μm~20μm,再更佳為6μm~10μm。
(具有熱硬化能之正型阻劑組成物) 作為具有熱硬化能之正型阻劑組成物,雖無特別限制,然而可舉出例如,含有鹼可溶性樹脂(A)與感光劑(B)之正型阻劑組成物。
[鹼可溶性樹脂(A)] 作為鹼可溶性樹脂,可採用任意具有對鹼具溶解性之鹼可溶性基之樹脂。 作為該鹼可溶性樹脂(A)(以下,亦記載為「共聚物(A)」),例如,係可適宜使用丙烯酸系樹脂。 作為丙烯酸系樹脂,較佳係含有由一般式(a-1)所表示之構成單元(A1)或含脂環式環氧基之單元(A3)。
[構成單元(A1)] 構成單元(A1)係由下述一般式(a-1)所表示。
[前述一般式中,R係表示氫原子或碳數1~5的烷基,Ra01
係表示氫原子或具有羥基之有機基]。
一般式(a-1)中,R係表示氫原子或碳數1~5的烷基。作為碳數1~5的烷基,碳數1~5的直鏈狀或分支鏈狀的烷基係較佳,具體而言,可列舉出甲基、乙基、丙基、異丙基、n-丁基、異丁基、tert-丁基、戊基、異戊基、新戊基等。 一般式(a-1)中,Ra01
係氫原子或具有羥基之有機基。 此處,所謂有機基,係可列舉出例如,分支狀、直鏈狀,或環狀的烷基、可具有置換基之芳基、可具有置換基之雜芳基、可具有置換基之芳烷基、或可具有置換基之雜芳烷基,Ra01
,係於其構造中至少具有一個羥基。前述有機基的碳數為1~20係較佳,6~12為更佳。碳數大則於保存安定性方面較佳,碳數小則解析性佳。
此外,作為構成單元(A1),Ra01
為氫原子的情況,亦即,選擇甲基丙烯酸或丙烯酸等雖亦在提高共聚物的鹼顯影性上為有效,然而由保存安定性方面來看,作為構成單元(A1),較佳係採用上述之具有羥基之有機基。
作為構成單元(A1)之較佳例,可舉出由下述一般式(a-1-1)所表示構成單元。
[前述一般式中,R係表示氫原子或碳數1~5的烷基,Ya01
係表示單鍵或碳數1~5的伸烷基,Ra001
係表示碳數1~5的烷基,a係表示1~5的整數,b係表示0或1~4的整數,a+b為5以下。此外,Ra001
為2以上存在之情況,此等的Ra001
係可相互相異亦可為相同]。
一般式(a-1-1)中,R係表示氫原子或碳數1~5的烷基,與前述為相同。一般式(a-1-1)中,R較佳為甲基。 又,Ya01
係表示單鍵或碳數1~5的直鏈狀或者分支狀的伸烷基。具體而言,可列舉出亞甲基、伸乙基、丙烯基、異丙烯基、n-丁烯基、異丁烯基、tert-丁烯基、戊烯基、異戊烯基、新戊烯基等。其中,較佳為單鍵、亞甲基、伸乙基。 Ya01
係由於可提高鹼可溶性及進一步提高作為層間絕緣膜時的耐熱性,故較佳為單鍵。
此處,a係表示1~5的整數,然而由易於製造的觀點來看,a較佳為1。又,於苯環上之羥基的鍵結位置係,將與Ya01
鍵結之碳原子作為基準(1號位置)時,較佳為鍵結於4號位置。
又,Ra001
為碳數1~5的直鏈狀或分支狀的烷基。具體而言,可列舉出甲基、乙基、丙基、異丙基、n-丁基、異丁基、tert-丁基、戊基、異戊基、新戊基等。其中由易於製造的觀點來看,較佳係為甲基或乙基。 此處,b係表示0或1~4的整數,然而由易於製造的觀點來看,b較佳係0。
作為構成單元(A1),更具體而言,可列舉出o-羥基苯基(甲基)丙烯酸酯、m-羥基苯基(甲基)丙烯酸酯、p-羥基苯基(甲基)丙烯酸酯、o-羥苄基(甲基)丙烯酸酯、m-羥苄基(甲基)丙烯酸酯、p-羥苄基(甲基)丙烯酸酯、o-羥基苯基乙基(甲基)丙烯酸酯、m-羥基苯基乙基(甲基)丙烯酸酯、p-羥基苯基乙基(甲基)丙烯酸酯等,較佳為p-羥基苯基(甲基)丙烯酸酯或p-羥苄基(甲基)丙烯酸酯,特佳為p-羥基苯基(甲基)丙烯酸酯。
共聚物中前述構成單元(A1)的含有比率較佳為10~70莫耳%。更加為15~60莫耳%,最佳為20~50莫耳%。
[含脂環式環氧基之單元(A3)] 又,作為含脂環式環氧基之單元(A3)若為構造中具有脂環式環氧基,且為由具有乙烯性雙鍵之化合物衍生之構成單元,則無特別限制。脂環式環氧基的脂環式基的碳數係較佳為5~10之程度。
作為具體的含脂環式環氧基之單元(A3),可列舉出例如,由以下一般式(1)~(31)所表示之含有脂環式環氧基之聚合性不飽和化合物所衍生者。
式中,R4
係表示氫原子或甲基,R5
係表示碳數1~8之2價之烴基,R6
係表示碳數1~20之2價之烴基,R4
、R5
及R6
可為相同或相異,w係表示0~10的整數。
此等之中,由一般式(1)~(6)、(14)、(16)、(18)、(21)、(23)~(25)、(30)所表示者為較佳。更佳為一般式(1)~(6)。
共聚物中,前述含脂環式環氧基之單元(A3)的含有比率較佳為5~40莫耳%。更佳為10~30莫耳%,最佳為15~25莫耳%。
[構成單元(A2)] 又,上述共聚物較佳係具有由一般式(a-2)所表示構成單元(A2)。
[R係表示氫原子或碳數1~5的烷基,Rb為烴基]。
前述一般式(a-2)中,R係表示氫原子或碳數1~5的烷基,與前述為相同。 作為Rb的烴基,可列舉出例如,分支狀、直鏈狀,或者環狀的烷基、可具有置換基之芳基、或可具有置換基之芳烷基。前述烴基的碳數較佳為1~20。此外,作為分支狀、直鏈狀的烷基,碳數1~12係較佳,最佳為1~6。作為環狀的烷基,碳數6~20係較佳,6~12係最佳。作為可具有置換基之芳基、或可具有置換基之芳烷基,碳數6~20係較佳,6~12係最佳。
作為構成單元(A2),具體而言可列舉出由甲基丙烯酸酯、乙基丙烯酸酯、丙基丙烯酸酯、異丙基丙烯酸酯、丁基丙烯酸酯、戊基丙烯酸酯、乙基己基丙烯酸酯、辛基丙烯酸酯、t-辛基丙烯酸酯等的直鏈或分支鏈烷基丙烯酸酯;環己基丙烯酸酯、二環戊基丙烯酸酯、2-甲基環己基丙烯酸酯、異莰基丙烯酸酯等的脂環式烷基丙烯酸酯;苄基丙烯酸酯、芳基丙烯酸酯(例如,苯基丙烯酸酯)等所衍生者。
或是,可列舉出由甲基甲基丙烯酸酯、乙基甲基丙烯酸酯、丙基甲基丙烯酸酯、異丙基甲基丙烯酸酯、n-丁基甲基丙烯酸酯、sec-丁基甲基丙烯酸酯、t-丁基甲基丙烯酸酯、戊基甲基丙烯酸酯、己基甲基丙烯酸酯、辛基甲基丙烯酸酯等的直鏈或分支鏈烷基甲基丙烯酸酯;環己基甲基丙烯酸酯、二環戊基甲基丙烯酸酯、2-甲基環己基甲基丙烯酸酯、異莰基甲基丙烯酸酯等的脂環式烷基甲基丙烯酸酯;苄基甲基丙烯酸酯、芳基甲基丙烯酸酯(例如甲基丙烯酸苯酯、甲基丙烯酸甲苯酯、甲基丙烯酸萘酯等)等所衍生者。
藉由將上述構成單元(A2)導入共聚物中,可調整共聚物的溶解速度。作為構成單元(A2),特別是由具有脂環式之基之單體所衍生者為較佳。
共聚物(A)中,構成單元(A2)的含有比率較佳為5~50莫耳%。
[構成單元(A4)] 又,在不違背本發明目的的範圍內,上述共聚物(A)中,可含有構成單元(A1)~(A3)以外的構成單元(A4)。此構成單元若為由具有乙烯性雙鍵之化合物衍生之構成單元則無特別限制。作為這樣的構成單元,可列舉出例如,選自由丙烯醯胺類、甲基丙烯醯胺類、烯丙基化合物、乙烯基醚類、乙烯基酯類、及苯乙烯類等之構成單元。
作為丙烯醯胺類,具體而言,可列舉出丙烯醯胺、N-烷基丙烯醯胺(烷基的碳數為1~10係較佳,可列舉出例如甲基、乙基、丙基、丁基、t-丁基、庚基、辛基、環己基、羥基乙基、苄基等)、N-芳基丙烯醯胺(作為芳基,係例如苯基、甲苯基、硝基苯基、萘基、羥基苯基等)、N,N-二烷基丙烯醯胺(烷基的碳數為1~10係較佳)、N,N-芳基丙烯醯胺(作為芳基,係例如有苯基)、N-甲基-N-苯基丙烯醯胺、N-羥基乙基-N-甲基丙烯醯胺、N-2-乙醯胺基乙基-N-乙醯基丙烯醯胺。
作為甲基丙烯醯胺類,具體而言可列舉出,甲基丙烯醯胺、N-烷基甲基丙烯醯胺(作為烷基,較佳係為碳數1~10者,例如可列舉出甲基、乙基、t-丁基、乙基己基、羥基乙基、環己基等)、N-芳基甲基丙烯醯胺(作為芳基,係有苯基等)、N,N-二烷基甲基丙烯醯胺(作為烷基,係有乙基、丙基、丁基等)、N,N-二芳基甲基丙烯醯胺(作為芳基,係有苯基等)、N-羥基乙基-N-甲基甲基丙烯醯胺、N-甲基-N-苯基甲基丙烯醯胺、N-乙基-N-苯基甲基丙烯醯胺。
作為烯丙基化合物,具體而言可列舉出,烯丙酯類(例如乙酸烯丙酯、己酸烯丙酯、辛酸烯丙酯、月桂酸烯丙酯、軟脂酸烯丙酯、硬脂酸烯丙酯、安息香酸烯丙酯、乙醯乙酸烯丙酯、乳酸烯丙酯等)、烯丙基羥乙基醚等。
作為乙烯基醚類,具體而言可列舉出,烷基乙烯基醚(例如,己基乙烯基醚、辛基乙烯基醚、癸基乙烯基醚、乙基己基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、氯乙基乙烯基醚、1-甲基-2,2-二甲基丙基乙烯基醚、2-乙基丁基乙烯基醚、羥基乙基乙烯基醚、二甘醇乙烯基醚、二甲基胺基乙基乙烯基醚、二乙基胺基乙基乙烯基醚、丁基胺基乙基乙烯基醚、苄基乙烯基醚、四氫糠基乙烯基醚等)、乙烯基芳基醚(例,如乙烯基苯基醚、乙烯基甲苯醚、乙烯基氯苯基醚、乙烯基-2,4-二氯苯基醚、乙烯基萘基醚、乙烯基蒽基醚等)。
作為乙烯基酯類,具體而言可列舉出,丁酸乙烯酯、異丁酸乙烯酯、乙烯基三甲基乙酸酯、乙烯基二乙基乙酸酯、戊酸乙烯酯、乙烯基己酸酯、乙烯基氯乙酸酯、乙烯基二氯乙酸酯、乙烯基甲氧基乙酸酯、乙烯基丁氧基乙酸酯、乙烯基苯乙酸酯、乙烯基乙醯乙酸酯、乙烯基乳酸酯、乙烯基-β-苯基丁酸酯、乙烯基苯甲酸酯、水楊酸乙烯酯、乙烯基氯苯甲酸酯、乙烯基四氯苯甲酸酯、乙烯基萘甲酸酯。
作為苯乙烯類,具體而言可列舉出,苯乙烯、烷基苯乙烯(例如甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基甲基苯乙烯等)、烷氧基苯乙烯(例如甲氧基苯乙烯、4-甲氧基-3-甲基苯乙烯、二甲氧基苯乙烯等)、鹵素苯乙烯(例如氯苯乙烯、二氯苯乙烯、三氯苯乙烯、四氯苯乙烯、五氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、氟苯乙烯、三氟苯乙烯、2-溴-4-三氟甲基苯乙烯、4-氟-3-三氟甲基苯乙烯等)。又,亦可列舉出丙烯腈、甲基丙烯腈等。
本實施形態中,共聚物(A)較佳係由前述構成單元(A1)、(A2)及(A3)所構成。 上述共聚物(A)的質量平均分子量(Mw:以凝膠滲透層析儀(GPC)之聚苯乙烯換算之測定值)較佳為2000~50000,更佳為5000~30000。藉由將分子量設定為2000以上,可容易地形成膜狀。又,藉由將分子量設為50000以下,可獲得適度的鹼溶解性。
上述共聚物係可藉由公知的自由基聚合來製造。亦即,可藉由將衍生出前述構成單元(A1)~(A3)等的聚合性單體及公知的自由基聚合起始劑溶解於聚合溶媒後,加熱攪拌來製造。
此外,鹼可溶性樹脂(A),係含有上述構成單元(A1)~(A3)之共聚物以外,亦可含有1種以上之其他共聚物。此共聚物係相對於上述共聚物(A)100質量份,較佳為0~50質量份,更佳為0~30質量份。此共聚物的質量平均分子量(Mw:以凝膠滲透層析儀(GPC)之聚苯乙烯換算之測定值)較佳為2000~50000,更佳為5000~30000。
[感光劑(B)] 作為本實施形態之感光劑(B),若為可作為感光成分使用之化合物則非受到特別限制者,然而作為較佳例可舉例為含醌二疊氮基之化合物。
作為含醌二疊氮基之化合物,具體而言可列舉出,酚化合物(亦稱為含酚性羥基之化合物)與萘醌二疊氮基磺酸化合物的完全酯化物或部分酯化物。
作為上述酚化合物,具體而言可列舉出2,3,4-三羥基二苯甲酮、2,3,4,4′-四羥基二苯甲酮等的多羥基二苯甲酮類;參(4-羥苯基)甲烷、雙(4-羥基-3-甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-2,3,5-三甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2,4-二羥基苯基甲烷、雙(4-羥基苯基)-3-甲氧基-4-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-4-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-3-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-2-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-3,4-二羥基苯基甲烷、4,4‘-[(3,4-二羥基苯基)亞甲基]雙(2-環己基-5-甲基酚)等的三苯酚型化合物;
2,4-雙(3,5-二甲基-4-羥苄基)-5-羥基酚、2,6-雙(2,5-二甲基-4-羥苄基)-4-甲基酚等的線型3核體酚化合物;1,1-雙[3-(2-羥基-5-甲苄基)-4-羥基-5-環己基苯基]異丙烷、雙[2,5-二甲基-3-(4-羥基-5-甲苄基)-4-羥基苯基]甲烷、雙[2,5-二甲基-3-(4-羥苄基)-4-羥基苯基]甲烷、雙[3-(3,5-二甲基-4-羥苄基)-4-羥基-5-甲基苯基]甲烷、雙[3-(3,5-二甲基-4-羥苄基)-4-羥基-5-乙基苯基]甲烷、雙[3-(3,5-二乙基-4-羥苄基)-4-羥基-5-甲基苯基]甲烷、雙[3-(3,5-二乙基-4-羥苄基)-4-羥基-5-乙基苯基]甲烷、雙[2-羥基-3-(3,5-二甲基-4-羥苄基)-5-甲基苯基]甲烷、雙[2-羥基-3-(2-羥基-5-甲苄基)-5-甲基苯基]甲烷、雙[4-羥基-3-(2-羥基-5-甲苄基)-5-甲基苯基]甲烷、雙[2,5-二甲基-3-(2-羥基-5-甲苄基)-4-羥基苯基]甲烷等的線型4核體酚化合物;2,4-雙[2-羥基-3-(4-羥苄基)-5-甲苄基]-6-環己基酚、2,4-雙[4-羥基-3-(4-羥苄基)-5-甲苄基]-6-環己基酚、2,6-雙[2,5-二甲基-3-(2-羥基-5-甲苄基)-4-羥苄基]-4-甲基酚等的線型5核體酚化合物等的線型多酚化合物;
雙(2,3,-三羥基苯基)甲烷、雙(2,4-二羥基苯基)甲烷、2,3,4-三羥基苯基-4′-羥基苯基甲烷、2-(2,3,4-三羥基苯基)-2-(2′,3′,4′-三羥基苯基)丙烷、2-(2,4-二羥基苯基)-2-(2′,4′-二羥基苯基)丙烷、2-(4-羥基苯基)-2-(4′-羥基苯基)丙烷、2-(3-氟-4-羥基苯基)-2-(3′-氟-4′-羥基苯基)丙烷、2-(2,4-二羥基苯基)-2-(4′-羥基苯基)丙烷、2-(2,3,4-三羥基苯基)-2-(4′-羥基苯基)丙烷、2-(2,3,4-三羥基苯基)-2-(4′-羥基-3′,5′-二甲基苯基)丙烷等的雙酚型化合物;1-[1-(4-羥基苯基)異丙基]-4-[1,1-雙(4-羥基苯基)乙基]苯、1-[1-(3-甲基-4-羥基苯基)異丙基]-4-[1,1-雙(3-甲基-4-羥基苯基)乙基]苯等的多核分支型化合物;1,1-雙(4-羥基苯基)環己烷等的縮合型酚化合物等。此等係可單獨或組合2種以上使用。
又,作為上述萘醌二疊氮基磺酸化合物,可列舉出萘醌-1,2-二疊氮基-5-磺酸或萘醌-1,2-二疊氮基-4-磺酸等。
又,其他的含醌二疊氮基之化合物,可列舉出例如鄰苯醌二疊氮基、鄰萘醌二疊氮基、鄰蒽醌二疊氮基或鄰萘醌二疊氮基磺酸酯類等的此等的核取代衍生物。進而,亦可使用鄰醌二疊氮基磺醯基氯,與,具有羥基或胺基之化合物(例如酚、p-甲氧基酚、二甲基酚、氫醌、雙酚A、萘酚、焦兒茶酚、苯三酚、苯三酚單甲醚、苯三酚-1,3-二甲醚、沒食子酸、剩餘一部份羥基而經酯化或醚化之沒食子酸、苯胺、p-胺基二苯基胺等)之反應生成物等。該等亦可單獨或將2種以上組合使用。
此等的含醌二疊氮基之化合物係可例如將三苯酚型化合物與萘醌-1,2-二疊氮基-5-磺醯基氯或萘醌-1,2-二疊氮基-4-磺醯基氯於二噁烷等適當的溶劑中,且於三乙醇胺、碳酸鹼、碳酸氫鹼等的鹼的存在下使其縮合,藉由完全酯化或部分酯化而製造。
又,作為上述(B)成分,較佳係使用非二苯甲酮系的含醌二疊氮基之化合物、較佳係使用多核分支型化合物。又,此含酚性羥基之化合物於350nm之波長之克吸光係數較佳為1以下。藉此,於感光性樹脂組成物中,可獲得更高之敏感度。
作為這樣的(B)成分,較佳係含醌二疊氮基之化合物,特佳係萘醌二疊氮基磺酸酯化物。其中,係可適宜使用4,4‘-[(3,4-二羥基苯基)亞甲基]雙(2-環己基-5-甲基酚)、1-[1-(4-羥基苯基)異丙基]-4-[1,1-雙(4-羥基苯基)乙基]苯等的萘醌二疊氮基磺酸酯化物。
(B)成分的含量係相對於全固體成分較佳為10~40質量%,更佳為15~30質量%。藉由使(B)成分的含量為10質量%以上,可使解析度提高。又,可使圖案形成後之圖案之膜減少量低減。又,藉由使(B)成分的含量為40質量%以下,可賦予適度的敏感度或透過率。
[有機溶劑(S)] 本實施形態之正型阻劑組成物,為了改善塗佈性並調整黏度,較佳係含有有機溶劑(S)。
作為(S)成分,可列舉出苯、甲苯、二甲苯、甲基乙基酮、丙酮、甲基異丁基酮、環己酮、甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、二甘醇、甘油、乙二醇單甲醚、乙二醇單***、丙二醇甲醚(PGME)、丙二醇單***、二甘醇單甲醚、二甘醇單***、二甘醇二甲醚、二甘醇二***、3-甲氧基丁基乙酸酯(MA)、3-甲氧基丁醇(BM)、3-甲基-3-甲氧基丁基乙酸酯、丙二醇甲醚醋酸酯(PGMEA)、丙二醇甲醚丙酸酯、丙二醇單***丙酸酯、碳酸甲酯、碳酸乙酯、碳酸丙酯、碳酸丁酯或此等的混合物等。其中較佳係使用PGME、PGMEA、MA或、PGME與PGMEA之混合溶劑、MA與BM之混合溶劑等。
有機溶劑(S)的使用量雖無特別限制,然而可以可塗佈於基板等之濃度,依據塗膜厚度作適當的選擇設定。具體而言,感光性樹脂組成物的固體成分濃度係為10~50質量%,特別是於15~35質量%之範圍內使用為較佳。
[任意成分] (黑色顏料) 本實施形態中,正型阻劑組成物係為了提高間隔壁的光吸收性,較佳為含有黑色顏料。 作為黑色顏料,可舉例為與上述黑色阻劑中之黑色顏料相同者。 使用黑色顏料之情況,黑色顏料的含量係相對於不揮發成分較佳為1%~10%。 藉由黑色顏料的含量介於上述範圍,可充分提高間隔壁的光吸收性。
(黃色顏料) 本實施形態中,正型阻劑組成物係為了防止因混入藍色(B)以外的次像素所造成之色純度的低下,故亦可含有黃色顏料。 作為黃色顏料,可列舉出C.I.顏料黃1(以下,皆同為「C.I.顏料黃」,故僅記載編號)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、185等。 使用黃色顏料之情況,黃色顏料的含量係相對於不揮發成分較佳為1%~10%。 藉由使黃色顏料的含量介於上述範圍內,可充分防止因混入藍色(B)以外的次像素所造成的色純度的低下。
(無機粒子) 本實施形態中,正型阻劑組成物係為了賦予間隔壁光散射性,亦可含有無機粒子。 作為無機粒子,例如,可使用玻璃、陶瓷(菫青石等)、金屬等。具體而言,可列舉出PbO-SiO2
系、PbO-B2
O3
-SiO2
系、ZnO-SiO2
系、ZnO-B2
O3
-SiO2
系、BiO-SiO2
系、BiO-B2
O3
-SiO2
系的硼矽酸鉛玻璃、硼矽酸鋅玻璃、硼矽酸鉍玻璃等的玻璃粉末,或氧化鈷、氧化鐵、氧化鉻、氧化鎳、氧化銅、氧化錳、氧化釹、氧化釩、氧化鈰提帕克(tipaque)黃、氧化鎘、氧化釕、二氧化矽、氧化鎂、尖晶石等Na、K、Mg、Ca、Ba、Ti、Zr、Al等的各氧化物,ZnO:Zn、Zn3
(PO4
)2
:Mn、Y2
SiO5
:Ce、CaWO4
:Pb、BaMgAl14
O23
:Eu、ZnS:(Ag, Cd)、Y2
O3
:Eu、Y2
SiO5
:Eu、Y3
A15
O12
:Eu、YBO3
:Eu、(Y, Gd)BO3
:Eu、GdBO3
:Eu、ScBO3
:Eu、LuBO3
:Eu、Zn2
SiO4
:Mn、BaAl12
O19
:Mn、SrAl13
O19
:Mn、CaAl12
O19
:Mn、YBO3
:Tb、BaMgAl14
O23
:Mn、LuBO3
:Tb、GdBO:Tb、ScBO3
:Tb、Sr6 Si3
O3
Cl4
:Eu、ZnS:(Cu, Al)、ZnS:Ag、Y2
O2
S:Eu、ZnS:Zn、(Y, Cd)BO3
:Eu、BaMgAl12
O23
:Eu等的螢光體粉末,鐵、鎳、鈀、鎢、銅、鋁、銀、金、白金等的金屬粉末等。 其中,二氧化矽、二氧化鈦(TiO2
)係較佳。 無機粒子的平均粒子徑較佳為0.1μm~1μm,更佳為0.2~0.5μm。無機粒子的平均粒子徑為上述範圍內,則可賦予間隔壁充分的光散射性。 使用無機粒子之情況,無機粒子的含量較佳係相對於鹼可溶性樹脂(A)100質量份為2~20%,更佳為5~10%。 無機粒子的含量為上述範圍內,則在維持微影性能的同時,亦可賦予間隔壁充分的光散射性。
[胺基甲酸酯寡聚物(U)] 本實施形態中,正型阻劑組成物係可含有具有2個以上聚合性官能基之胺基甲酸酯寡聚物(U)。 作為胺基甲酸酯寡聚物(U),較佳係具有胺基甲酸酯鍵結之(甲基)丙烯酸酯化合物,更佳係官能基數為3以上之胺基甲酸酯(甲基)丙烯酸酯。 所謂官能基數為3以上之胺基甲酸酯(甲基)丙烯酸酯,係指分子中具有胺基甲酸酯鍵結(-NH-CO-O-)及3個以上之(甲基)丙烯醯氧基者。胺基甲酸酯(甲基)丙烯酸酯的官能基數,較佳係3以上,更佳係3~10,再更佳為3~5,特佳為3或4,最佳為3(亦即,官能基數為3之胺基甲酸酯(甲基)丙烯酸酯)。 使用胺基甲酸酯寡聚物(U)之情況,胺基甲酸酯寡聚物(U)的含量係相對於鹼可溶性樹脂(A)100質量%,較佳為5質量%以上,更佳為10~60質量%,再更佳為20~50質量%。 [(F)成分] 本實施形態中,為了賦予阻劑膜撥水性,正型阻劑組成物係可含有氟添加劑(以下亦稱為「(F)成分」)。 阻劑膜若具有撥水性,則以噴墨方式形成色彩濾波器之情況中,可防止噴墨混入其他的次像素中。 作為(F)成分,可使用例如,日本特開2010-002870號公報、日本特開2010-032994號公報、日本特開2010-277043號公報、日本特開2011-13569號公報、日本特開2011-128226號公報中所記載的含氟高分子化合物。
又,作為本實施形態之正型阻劑組成物之其他的任意成分,可列舉出例如,反應促進劑、矽烷偶合劑、界面活性劑、熱酸產生劑、架橋劑、敏化劑、消泡劑等的各種添加劑。
<步驟(C)> 步驟(C)中,將前述阻劑膜3由前述透明基板1側進行曝光(圖1(e))。藉由由透明基板1側進行曝光,黑色矩陣2a係作為遮罩而作用,且僅曝光阻劑膜3與透明基板1之間黑色矩陣2a未形成的領域,而可形成鹼可溶性領域3a。 曝光係,例如對於阻劑膜3,藉由由透明基板1側照射紫外線、準分子雷射光等的活性能量射線而進行。 作為此活性能量射線的光源,可列舉出例如低壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、準分子雷射發生裝置、YAG之3倍、半導體雷射之2倍波等的UV雷射等。 所照射之能量射線量雖係因正型阻劑組成物的組成而有所不同,然而只要為例如30~2000mJ/cm2
即可。
<步驟(D)> 步驟(D)中,將前述曝光後之阻劑膜3顯影後,形成阻劑圖案。藉由顯影,鹼可溶性領域3a係被去除,且於黑色矩陣2a上形成阻劑圖案3b(間隔壁圖案3b)。 作為鹼顯影中所使用之顯影液,可列舉出如四甲基氫氧化銨(TMAH)水溶液的有機鹼水溶液,或氫氧化鈉、氫氧化鉀、偏矽酸鈉、磷酸鈉等的無機鹼水溶液。
<任意步驟> <步驟(E)> 本實施形態之間隔壁用圖案的形成方法,係可更進一步具有將前述阻劑圖案3b熱硬化之步驟(E)。 前述阻劑圖案之加熱,係例如於300℃以下的溫度條件下進行,較佳係於90~250℃下進行。本實施形態中,於更低的溫度條件下可簡單地硬化,較佳係可於220℃以下簡單地進行硬化。 由保持阻劑圖案的垂直性之觀點,步驟(E)之熱硬化較佳係以2階段以上進行。將熱硬化以2階段以上進行之情況,較佳係於每階段提高熱硬化溫度。例如,以90~150℃加熱20~40分鐘之後,可以180~300℃加熱50~70分鐘。
<步驟(C1)> 本實施形態之間隔壁用圖案的形成方法,依據需要,於步驟(C)與步驟(D)之間可具有進行加熱處理(曝光後加熱處理)之步驟(C1)。
本實施形態中,將具有熱硬化能之正型阻劑組成物塗佈於黑色矩陣圖案上,並由透明基板側進行曝光。因此,黑色矩陣圖案係作為遮罩而作用,且可形成與黑色矩陣圖案之對準精度良好阻劑圖案(間隔壁)。 又,本實施形態之間隔壁用圖案的形成方法,係特別對於嵌入有量子點螢光體之顯示元件之間隔壁用圖案之形成為有用。 使用量子點螢光體之情況,係要求對有機液體之溶解耐性。本實施形態中,由於使用具有熱硬化能之正型阻劑組成物,故所形成之間隔壁圖案對於有機液體具有優良的溶解耐性。 又,依據本實施形態,可形成對於透明基板垂直性高之形狀之間隔壁用圖案。 [實施例]
以下,藉由實施例更進一步詳細地說明本發明,然而本發明並非受到此等例子所限制者。
(實施例1) <阻劑的調整> 以甲基丙烯酸4-羥基苯酯:40重量份、甲基丙烯酸甲酯:40重量份、3,4-環氧環己基甲基甲基丙烯酸酯:20重量份的比例混合,於有機溶媒(PGMEA)中進行自由基聚合,獲得聚合物A。 相對於由上述所獲得之聚合物溶液的固體成分75重量份,將於4,4’-[(3,4-二羥基苯基)亞甲基]雙(2-環己基-5-甲基酚)中使萘醌二疊氮基-5-磺酸酯反應後之產物(酯化率80%)25重量份,與作為溶劑分以使其成為PGMEA/ PGME=60/40的比例添加200質量份之PGMEA與PGME,獲得阻劑A。
<圖案的形成> 於玻璃基板上將黑色阻劑(製品名:CFPR BK-461;東京應化工業製)藉由旋塗法以使膜厚成為2.0μm之方式塗佈,並以100℃進行2分鐘之烘烤處理。於此基板介隔光罩,以超高壓水銀燈150mJ/cm2
的光量曝光,以0.04%KOH水溶液進行顯影、水洗、熱固化,獲得形成有利用黑色光阻所形成之遮光層(黑色矩陣圖案)之基板。於形成此遮光層之面上將阻劑A藉由旋塗法以厚度為10μm之方式塗佈,並將由高壓水銀燈獲得之紫外線由基板面側以1000mJ/cm2
照射。之後藉由TMAH2.38%水溶液進行2次1分鐘之顯影,再以加熱板進行(1)100℃、30分鐘,(2)120℃、30分鐘,(3)200℃、60分鐘之3階段烘烤作為熱固化。此結果,阻劑A係以垂直性高的形狀,解析至5μm的圖案大小。又,阻劑圖案係以與黑色矩陣圖案之對準精度良好地形成。 將此經圖案化之基板浸漬於PGMEA中1分鐘,然而並沒有觀察到阻劑形狀的變化。
(實施例2) <阻劑的調整> 於實施例1所調製之阻劑A中,將阻劑A的不揮發成分100重量份與二氧化矽粒子(粒徑300nm)100重量份與PGME100重量份混合後,以行星式攪拌機攪拌,獲得阻劑B。
<圖案的形成> 於與實施例1相同之黑色阻劑經圖案化之基板上塗佈阻劑B,以700mJ/cm2
進行曝光、顯影、熱固化。此結果,阻劑B係解析至最小之大小為8μm止。又,阻劑圖案係以與黑色矩陣圖案之對準精度良好地形成。
(比較例1) 於與實施例1相同之黑色阻劑經圖案化之基板上將正型阻劑(製品名:PMER P-7130;東京應化工業製)藉由旋塗法以厚度為2.0μm進行塗佈,並將由高壓水銀燈獲得之紫外線由基板面側以300mJ/cm2
照射,藉由TMAH2.38%水溶液進行顯影。將此經圖案化之基板浸漬於PGMEA中1分鐘後,阻劑係完全剝離。
(比較例2) 於與實施例1相同之黑色阻劑經圖案化之基板上將正型阻劑(製品名:PMER P-7130;東京應化工業製)的高濃度品(固體成分濃度35%)藉由旋塗法以厚度為10μm進行塗佈,並將由高壓水銀燈獲得之紫外線由基板面側以1000mJ/cm2
照射,藉由TMAH2.38%水溶液進行顯影。接著,以加熱板進行(1)100℃、30分鐘,(2)120℃、30分鐘,(3)200℃、60分鐘之3階段烘烤作為熱固化。此結果,阻劑形狀係成為自基板界面為強烈的錐角之鏡片形狀。 又,將此經圖案化之基板浸漬於PGMEA中1分鐘後,確認到阻劑膜厚減少。
(比較例3) 於與實施例1相同之黑色阻劑經圖案化之基板上,塗佈由實施例2所作成之阻劑B。阻劑B係介隔黑色阻劑經圖案化之遮罩,由阻劑B面側(與基板面為相反側)以700mJ/cm2
曝光,藉由TMAH2.38%水溶液進行1分鐘之顯影。之後實施例1同樣地進行顯影、熱固化。其結果,遮罩中之最大之100μm大小的圖案亦無法解析。 再將阻劑B曝光時,雖然嘗試對準下方之黑色阻劑圖案與遮罩,然而由於阻劑B為強烈的白色,故與黑色阻劑圖案及遮罩的位置對準係為困難。
1‧‧‧透明基板2‧‧‧塗膜2a‧‧‧黑色矩陣3‧‧‧阻劑膜3a‧‧‧鹼可溶性領域3b‧‧‧阻劑圖案(間隔壁圖案)
[圖1]係說明間隔壁用圖案形成方法之一實施形態之概略步驟圖。
Claims (5)
- 一種間隔壁用圖案的形成方法,其係次像素的至少一部份中嵌入有色別發光體之顯示元件之間隔壁用圖案的形成方法,具有於透明基板上圖案化黑色阻劑之步驟(A),及將具有熱硬化能之正型阻劑組成物塗佈於前述黑色阻劑經圖案化之前述透明基板上,形成阻劑膜之步驟(B),及將前述黑色阻劑作為遮罩,由前述透明基板之形成有前述黑色阻劑之圖案之面之相反面側,僅將前述阻劑膜之前述阻劑膜與前述透明基板之間未形成前述黑色矩陣的領域進行曝光之步驟(C),及將前述曝光後之阻劑膜進行顯影,並將前述阻劑膜之曝光部去除,於前述黑色矩陣上形成阻劑圖案之步驟(D),其中,前述正型阻劑組成物係含有鹼可溶性樹脂(A)與感光劑(B),前述鹼可溶性樹脂(A)係包含選自由下述一般式(a-1)所表示之構成單元(A1)及含脂環式環氧基之單元(A3)所成之群組中選出之至少1種,
- 如請求項1所記載之間隔壁用圖案的形成方法,其中,更進一步具有將前述阻劑圖案熱硬化之步驟(E)。
- 如請求項1所記載之間隔壁用圖案的形成方法,其中,前述色別發光體係量子點螢光體。
- 如請求項1所記載之間隔壁用圖案的形成方法,其中,前述阻劑膜的膜厚為6μm以上。
- 如請求項1~4任一項所記載之間隔壁用圖案的形成方法,其中,前述正型阻劑組成物係更進一步含有平均粒子徑0.1~1μm的無機粒子。
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