TWI736521B - 平坦化膜用或微透鏡用樹脂組成物 - Google Patents
平坦化膜用或微透鏡用樹脂組成物 Download PDFInfo
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- TWI736521B TWI736521B TW104122318A TW104122318A TWI736521B TW I736521 B TWI736521 B TW I736521B TW 104122318 A TW104122318 A TW 104122318A TW 104122318 A TW104122318 A TW 104122318A TW I736521 B TWI736521 B TW I736521B
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
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- 125000000217 alkyl group Chemical group 0.000 claims description 3
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- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
- C08F12/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract
Description
本發明係關於熱硬化性之平坦化膜用或微透鏡用樹脂組成物,及使用該樹脂組成物的平坦化膜之製作方法及微透鏡之製作方法。
於製造CCD/CMOS影像感測器的步驟中,係進行以溶劑、鹼溶液等所致之浸漬處理,為了防止藉由如此之處理使元件劣化或損傷,而進行於元件表面設置對於該處理具有耐性的保護膜。於如此之保護膜係要求具有透明性、耐熱性及耐光性高,長期間不會引起著色等之變質、為耐溶劑性、耐鹼性優異者等之性能(專利文獻1)。進而,近年來,由於隨著CCD/CMOS影像感測器之高精細化而必須提昇感測器感度,因此在為了從微透鏡效率佳地聚光於受光部而於彩色濾光片上等形成保護膜的情況,該保護膜亦被要求可使形成於底層基板上的段差予以平坦化(專利文獻2至4)。又,亦進行由如此之保護膜製作微透鏡。
作為CCD/CMOS影像感測器用微透鏡之製作方法之一,已知有回蝕法(專利文獻5及專利文獻6)。亦即,於形成在彩色濾光片上的微透鏡用樹脂膜上形成阻劑圖型,藉由熱處理使此阻劑圖型回流而形成透鏡圖型。將此使阻劑圖型回流所形成的透鏡圖型作為蝕刻遮罩,將底層之微透鏡用樹脂膜進行回蝕,將透鏡圖型形狀轉印於微透鏡用樹脂膜,藉此而製作微透鏡。
另一方面,於CCD/CMOS影像感測器用之彩色濾光片中,在以往之顏料分散系統中,使解像度更為提昇一事係為困難,且因顏料的粗大粒子而發生色不均等之問題,因此並不適於如固體攝像元件般地要求微細圖型的用途。因此,提案有取代顏料分散系而使用染料的技術(專利文獻7)。然而,由於以往之熱硬化性的保護膜係以180℃以上之溫度進行燒成,因此一般而言,對於使用了在180℃左右會開始分解的染料之彩色濾光片上的適用係有困難(專利文獻8)。
[專利文獻1]日本專利第2921770號
[專利文獻2]國際公開第2013/005619號
[專利文獻3]日本特開2008-31417號公報
[專利文獻4]日本特開2006-113547號公報
[專利文獻5]日本特開平1-10666號公報
[專利文獻6]日本特開平6-112459號公報
[專利文獻7]日本特開平6-75375號公報
[專利文獻8]日本特開2010-237374號公報
於本發明中係根據前述情事而完成者,該所欲解決之課題係提供一種透明性、耐溶劑性及平坦性優異之以高於100℃的所期望之溫度可硬化的熱硬化性之樹脂組成物。
本發明者們為了解決前述之課題而進行努力探討的結果,因而完成本發明。
(式中,R0各自獨立表示氫原子或甲基;R1表示單鍵
或碳原子數1至5之伸烷基,該伸烷基亦可於其主鏈具有醚鍵;R2表示環氧基,或者具有環氧環之碳原子數5至12之有機基)。
(式中,R0表示氫原子或甲基;R1表示單鍵或碳原子數1至5之伸烷基,該伸烷基亦可於其主鏈具有醚鍵)。作為第3觀點,如第1觀點或第2觀點之平坦化膜用或微透鏡用樹脂組成物,其中,前述共聚物係進一步為具有以下述式(3)所表示之構造單位的共聚物,
(式中,R0表示氫原子或甲基;R3表示氫原子、碳原子數1至10之烷基、碳原子數1至10之烷氧基、氰基、羧基、苯基或鹵素基)。
作為第4觀點,如第1觀點至第3觀點中任一觀點之平坦化膜用或微透鏡用樹脂組成物,其係進一步含有促進前述共聚物之硬化的觸媒。
作為第5觀點,如第1觀點至第4觀點中任一觀點之平坦化膜用或微透鏡用樹脂組成物,其中,前述觸媒基於從前述樹脂組成物排除前述溶劑後的固體成分中之含量,係包含0.1質量%至20質量%。
作為第6觀點,如第1觀點至第5觀點中任一觀點之平坦化膜用或微透鏡用樹脂組成物,其中,前述共聚物之重量平均分子量為1,000至50,000。
作為第7觀點,一種平坦化膜之製作方法,其係將如第1觀點至第6觀點中任一觀點之樹脂組成物塗佈於基板上,並以高於100℃、未達180℃之溫度進行烘烤。
作為第8觀點,如第7觀點之平坦化膜之製作方法,其係於前述基板上形成彩色濾光片,並於該彩色濾光片上塗佈前述樹脂組成物。
作為第9觀點,一種微透鏡之製作方法,其係將如第1觀點至第6觀點中任一觀點之樹脂組成物塗佈於形成有彩色濾光片的基板上,並以高於100℃、未達180℃之溫度進行烘烤而形成樹脂膜,於前述樹脂膜上形成阻劑圖型,將前述阻劑圖型進行回流而形成透鏡圖型,將前述透
鏡圖型作為蝕刻遮罩來將前述樹脂膜進行回蝕。
本發明之樹脂組成物,由於該組成物中所包含的共聚物具有環氧基或環氧環與羥基之自我交聯型,因此並不一定要添加交聯劑,且具有高於100℃、未達180℃之所期望的溫度,例如140℃之熱硬化性。進而,由本發明之樹脂組成物所形成的樹脂膜係具有優異的透明性、耐溶劑性、及平坦性。由以上可知,藉由由本發明之樹脂組成物所形成的樹脂膜,可將形成於底層基板上的段差予以平坦化。又,在由本發明之樹脂組成物形成樹脂膜後塗佈阻劑的情況,及在平坦化膜或微透鏡形成後進行電極/配線形成步驟的情況,前述樹脂膜亦可使所謂與阻劑之混合、因有機溶劑導致之平坦化膜或微透鏡之變形及剝離的問題明顯減少。因而,本發明之樹脂組成物係適合作為形成平坦化膜及微透鏡的材料。
1‧‧‧段差基板
2‧‧‧樹脂膜
3‧‧‧線寬
4‧‧‧線間間隔
h1‧‧‧段差基板之段差
h2‧‧‧樹脂膜之段差
[第1圖]係顯示於段差基板上塗佈本發明之樹脂組成物,並進行烘烤所形成的樹脂膜之示意圖。
以下,說明本發明之各成分的詳細內容。從
本發明之樹脂組成物排除溶劑後的固體成分通常為1質量%至50質量%。
本發明之樹脂組成物中所包含的共聚物係前述之具有以下述式(1)所表示的構造單位及以式(2)所表示的構造單位之共聚物。
(式中,R0各自獨立表示氫原子或甲基;R1表示單鍵或碳原子數1至5之伸烷基,該伸烷基亦可於其主鏈具有醚鍵;R2表示環氧基,或者具有環氧環之碳原子數5至12之有機基)。
作為前述式(1)的例子係可列舉下述以式(1-1)或式(1-2)所表示的構造單位。
(式中,R0表示氫原子或甲基;R1表示單鍵或碳原子數1至5之伸烷基)。
前述共聚物係可進一步為具有以下述式(3)所表示的構造單位之共聚物。
(式中,R0表示氫原子或甲基;R3表示氫原子、碳原子數1至10之烷基、碳原子數1至10之烷氧基、氰基、羧基、苯基或鹵素基)。
作為形成以前述式(3)所表示的構造單位之化合物(單體)的具體例係可列舉:苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-tert-丁基苯乙烯、4-甲氧基苯乙烯、4-氰基苯乙烯、4-乙烯基苯甲酸、4-乙烯基聯苯、4-氟苯乙烯、4-氯苯乙烯、4-溴苯
乙烯。此等係可單獨使用,亦可將2種以上組合使用。
於前述共聚物中,以上述式(1)所表示的構造單位之含量係例如10mol%至90mol%,較佳為20mol%至70mol%。又,以上述式(2)所表示的構造單位之含量係例如10mol%至90mol%,較佳為20mol%至80mol%。在前述共聚物進一步具有以上述式(3)所表示的構造單位時,該含量係例如10mol%至90mol%,較佳為20mol%至70mol%。
前述共聚物之重量平均分子量通常為1,000至50,000,較佳為3,000至30,000。另外,重量平均分子量係藉由凝膠滲透層析法(GPC),使用聚苯乙烯作為標準試料所得到的值。
又,本發明之樹脂組成物中之前述共聚物的含量,係基於該樹脂組成物之固體成分中的含量,通常為1質量%至99質量%,較佳為5質量%至95質量%。
於本發明中,得到前述共聚物的方法雖無特別限定,但一般而言,係藉由使包含為了得到上述共聚物所使用之單體種的單體混合物在聚合溶劑中、通常50℃至120℃之溫度下進行聚合反應而得到。如此方式所得到的共聚物,通常為溶解於溶劑中的溶液狀態,以此狀態不進行分離而使用於本發明之樹脂組成物亦可。
又,可藉由將如上述方式所得到的共聚物之溶液投入經攪拌的己烷、二乙基醚、甲醇、水等之不良溶劑,使該共聚物進行再沉澱,將所生成的沉澱物進行過濾
/洗淨之後,在常壓或減壓下,進行常溫或者加熱乾燥,而將該共聚物製成粉體。可藉由如此之操作,而將與前述共聚物共存的聚合起始劑或未反應化合物進行去除。於本發明中係可將前述共聚物之粉體直接使用,或者,亦可使該粉體再溶解於例如後述之溶劑中成為溶液的狀態來進行使用。
<硬化促進觸媒>
本發明之樹脂組成物中所包含的觸媒係促進前述共聚物之硬化的觸媒,有時亦稱為硬化促進觸媒或者硬化促進劑,可使用1,8-二氮雜雙環[5.4.0]十一烯-7及其之有機酸鹽、咪唑類、膦類、鏻鹽。
[0021]作為硬化促進觸媒之市售品係可列舉例如:DBU[註冊商標]、U-CAT[註冊商標]SA 1、U-CAT[註冊商標]SA 102、U-CAT[註冊商標]SA 106、U-CAT[註冊商標]SA 506、U-CAT[註冊商標]SA 603(以上,SAN-APRO(股)製)、CUREZOL[註冊商標]2E4MZ(四國化成工業(股)製)、HOKKO TPP[註冊商標]、TPP-MK[註冊商標](以上,北興化學工業(股)製)。此等之硬化促進觸媒係可單獨或將2種以上組合使用。
本發明之樹脂組成物中之硬化促進觸媒的含量,係基於該樹脂組成物之固體成分中的含量,通常為0.1質量%至20質量%。
本發明之樹脂組成物的調製方法雖無特別限定,但可列舉例如,將前述共聚物溶解於溶劑中,於此溶液中以特定比例混合前述硬化促進觸媒,而製成均勻的溶液之方法。進而,可列舉於此調製方法之適當的階段中,因應需要而進一步添加其他的添加劑來進行混合之方法。
作為前述溶劑係只要將前述共聚物及前述硬化促進觸媒進行溶解者則無特別限定。作為如此之溶劑係可列舉例如:乙二醇單甲基醚、乙二醇單乙基醚、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單甲基醚乙烯酯、丙二醇丙基醚乙烯酯、丙二醇單丁基醚、丙二醇單丁基醚乙烯酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、2-庚酮、γ-丁內酯。此等之溶劑係可單獨使用,亦可將2種以上組合使用。
此等之溶劑之中,就提昇將本發明之樹脂組成物塗佈於基板上所形成的塗膜之平坦性的觀點而言,較佳為丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、2-庚酮、乳酸乙酯、乳酸丁酯及環己酮。
又,本發明之樹脂組成物亦可在提昇塗佈性的目的下而含有界面活性劑。作為該界面活性劑係可列舉例如:聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯
鯨蠟醚、聚氧乙烯油基醚等之聚氧乙烯烷基醚類、聚氧乙烯辛苯基醚、聚氧乙烯壬苯基醚等之聚氧乙烯烷基芳基醚類、聚氧乙烯.聚氧丙烯嵌段共聚物類、山梨醇酐單月桂酸酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯、山梨醇酐單油酸酯、山梨醇酐三油酸酯、山梨醇酐三硬脂酸酯等之山梨醇酐脂肪酸酯類、聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單棕櫚酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚氧乙烯山梨醇酐三油酸酯、聚氧乙烯山梨醇酐三硬脂酸酯等之聚氧乙烯山梨醇酐脂肪酸酯類等之非離子系界面活性劑、EFTOP[註冊商標]EF301、同EF303、同EF352(以上,Mitsubishi Materials Electronic Chemicals(股)製)、MEGAFAC[註冊商標]F-171、同F-173、同R-30、同R-40、同R-40-LM(以上,DIC(股)製)、Fluorad FC430、同FC431(以上,住友3M(股)製)、AsahiGuard[註冊商標]AG710、SURFLON[註冊商標]S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(股)製)、FTX-206D、FTX-212D、FTX-218、FTX-220D、FTX-230D、FTX-240D、FTX-212P、FTX-220P、FTX-228P、FTX-240G、DFX-18等FTERGENT系列((股)Neos製)等之氟系界面活性劑、有機矽氧烷聚合物KP341(信越化學工業(股)製)。此等之界面活性劑係可單獨使用,亦可將2種以上組合使用。
又,在使用前述界面活性劑的情況,本發明之樹脂組成物中的含量,係基於該樹脂組成物之固體成分
中的含量,為0.001質量%至3質量%以下,較佳為0.01質量%至1質量%以下,更佳為0.05質量%至0.5質量%以下。
又,本發明之樹脂組成物係在不損及本發明之效果的範圍內,可因應需要而包含交聯劑、紫外線吸收劑、增感劑、可塑劑、抗氧化劑、密著助劑等之添加劑。
以下,針對本發明之樹脂組成物的使用例進行說明。
於基板{例如,以氧化矽膜所被覆的矽等之半導體基板、以氮化矽膜或氧化氮化矽膜所被覆的矽等之半導體基板、形成有彩色濾光片的矽等之半導體基板、氮化矽基板、石英基板、玻璃基板(包含無鹼玻璃、低鹼玻璃、結晶化玻璃)、形成有ITO膜的玻璃基板}上,藉由旋轉器、塗佈機等之適當的塗佈方法塗佈本發明之樹脂組成物後,使用加熱板等之加熱手段進行烘烤使其硬化,而形成平坦化膜或微透鏡用樹脂膜。
烘烤條件係由烘烤溫度80℃至300℃,烘烤時間0.3分鐘至60分鐘當中適當選擇。又,以上述溫度範圍內之不同的烘烤溫度進行2階段以上處理亦可。在本發明之樹脂組成物的情況中,可以未達180℃之烘烤溫度形成所期望的樹脂膜。
又,作為由本發明之樹脂組成物所形成的樹脂膜之膜厚係0.005μm至5.0μm,較佳為0.01μm至3.0μm。
其後,於由本發明之樹脂組成物所形成的微透鏡用樹脂膜之上塗佈阻劑溶液,通過特定的遮罩進行曝光,因應需要而進行曝光後加熱(PEB),進行鹼顯像、清洗及乾燥,藉此而形成特定的阻劑圖型。於曝光係可使用例如:g線、i線、KrF準分子雷射、ArF準分子雷射。
接著,藉由進行加熱處理(通常以不超過200℃的溫度),將上述阻劑圖型進行回流而形成透鏡圖型。將此透鏡圖型作為蝕刻遮罩,將底層之微透鏡用樹脂膜進行回蝕,將透鏡圖型形狀轉印於微透鏡用樹脂膜,藉此而製作微透鏡。
以下,雖列舉實施例更詳細地說明本發明,但本發明並不僅限定於此等之實施例。
裝置:日本分光(股)製GPC系統
管柱:Shodex[註冊商標]KF/804L及KF-803L
管柱烘箱:40℃
流量:1mL/分
溶離液:四氫呋喃
以下之實施例中所使用的簡稱之意思係如下所述。
GMA:甲基丙烯酸環氧丙酯
4-HS:4-羥基苯乙烯
St:苯乙烯
TPP:三苯基膦
jER828:三菱化學(股)製環氧樹脂jER[註冊商標]828(商品名)
DFX-18:(股)Neos製界面活性劑FTERGENT[註冊商標]DFX-18(商品名)
PGME:丙二醇單甲基醚
PGMEA:丙二醇單甲基醚乙酸酯
按照如下表1所示之組成,來混合共聚物、交聯劑、硬化促進觸媒、界面活性劑及溶劑而製成均勻的溶液。另外,實施例1係不使用交聯劑及硬化促進觸媒,實施例2係不使用交聯劑,實施例3係未使用交聯劑及交聯促進觸媒。然後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾而調製出樹脂組成物。
使用旋轉塗佈機,將實施例1至實施例3及比較例1所調製出的樹脂組成物分別塗佈於矽晶圓上,於加熱板上以100℃ 1分鐘,進而以140℃ 10分鐘進行烘烤,而形成膜厚0.6μm之樹脂膜。對於此等之樹脂膜,進行於丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、環己酮、乳酸乙酯、乙酸丁酯、丙酮、γ-丁內酯、甲基乙基酮、2-庚酮、2-丙醇、及2.38質量%濃度之氫氧化四甲基銨(TMAH)水溶液中,分別在23℃之溫度條件下,浸漬5分鐘之試驗。於浸漬前後測定膜厚變化,在上述浸漬溶劑之
中即使是1個對於浸漬前之膜厚而言有5%以上之膜厚增減的情況便將耐溶劑性評估為「×」,在針對所有的溶劑而膜厚增減未達5%的情況係將耐溶劑性評估為「○」。將評估結果顯示於表2。
使用旋轉塗佈機,將實施例1至實施例3所調製出的樹脂組成物分別塗佈於石英基板上,於加熱板上以100℃ 1分鐘,進而以140℃ 10分鐘進行烘烤,而形成膜厚0.6μm之樹脂膜。對於此等之樹脂膜,使用紫外線可見分光光度計UV-2550((股)島津製作所製),來測定波長400nm之透過率。將評估結果顯示於表2。
藉由使用旋轉塗佈機,將實施例1至實施例3所剛調製出的樹脂組成物分別塗佈於矽晶圓上,於加熱板上以100℃ 1分鐘,進而以140℃ 10分鐘進行烘烤而形成樹脂膜,使用光干擾式膜厚測定裝置Lambda Ace VM/2110(大日本SCREEN製造(股)製),來測定此等之樹脂膜的膜厚。進而,將相同的樹脂組成物以35℃(加速試驗)保管1個月,測定由保管後之樹脂組成物以相同的方法所形成之樹脂膜的膜厚。與由剛調製之樹脂組成物所形成的樹脂膜之膜厚進行比較,將膜厚變化未達10%者視為「○」,將10%以上者視為「×」。將評估結果顯示於表
2。
使用旋轉塗佈機,將實施例1至實施例3所調製出的樹脂組成物分別塗佈於高度0.3μm、線寬10μm、線間間隔10μm之段差基板(參照第1圖)上,於加熱板上以100℃ 1分鐘,進而以140℃ 10分鐘進行烘烤,而形成膜厚0.6μm之樹脂膜。由第1圖所示之h1(段差基板1之段差)與h2(樹脂膜2之段差,亦即線上之樹脂膜的高度與間隔上之樹脂膜的高度之高低差),使用「式:(1-(h2/h1))×100」來求出平坦化率。將評估結果顯示於表2。
於乾蝕刻速率之測定中所使用的蝕刻器及蝕刻氣體係如以下所述。
蝕刻器:RIE-10NR(SAMCO(股)製)
蝕刻氣體:CF4
使用旋轉塗佈機,將實施例1至實施例3所調製出的樹脂組成物分別塗佈於矽晶圓上,於加熱板上以100℃ 1分鐘,進而以140℃ 10分鐘進行烘烤,而形成膜厚0.6μm之樹脂膜。使用前述蝕刻器及蝕刻氣體,來測定此等之膜的乾蝕刻速率。相同地,使用旋轉塗佈機,將阻劑溶液(THMR-iP800(東京應化工業(股)製))塗佈於矽晶
圓上,於加熱板上以90℃ 1.5分鐘進行烘烤,形成膜厚1μm之阻劑膜,而測定出乾蝕刻速率。接著,求出由實施例1至實施例3所調製出的樹脂組成物所得到的膜對前述阻劑膜之乾蝕刻速率比。將評估結果顯示於表2。
由表2的結果可知,由本發明之樹脂組成物所形成的樹脂膜為高耐溶劑性並且高透明性。進而可知,本發明之樹脂組成物係保存安定性優異。又,由本發明之樹脂組成物所形成的樹脂膜係具有平坦化率50%以上之段差平坦化性者。進而,於以回蝕法所致之微透鏡製作中,將透鏡圖型的形狀忠實地轉印於底層的樹脂膜時,可求出阻劑膜之乾蝕刻速率X與樹脂膜之乾蝕刻速率Y為相等(X:Y=1:0.8~1.2),成為由本發明之樹脂組成物所形成的樹脂膜皆滿足此的結果。另一方面,關於由比較例1調製出的樹脂組成物所形成之樹脂膜,係成為不滿足耐溶劑性的結果,故可知於平坦化膜用及微透鏡用任一者皆不適合。
1‧‧‧段差基板
2‧‧‧樹脂膜
3‧‧‧線寬
4‧‧‧線間間隔
h1‧‧‧段差基板之段差
h2‧‧‧樹脂膜之段差
Claims (9)
- 如請求項1或2之熱硬化性之平坦化膜用或微透鏡用樹脂組成物,其中,促進前述共聚物之硬化的觸媒為三苯基膦。
- 如請求項1或2之熱硬化性之平坦化膜用或微透鏡用樹脂組成物,其中,前述觸媒基於從前述樹脂組成物排除前述溶劑後的固體成分中之含量,係包含0.1質量%至 20質量%。
- 如請求項1或2之熱硬化性之平坦化膜用或微透鏡用樹脂組成物,其中,前述共聚物之重量平均分子量為1,000至50,000。
- 如請求項7之平坦化膜之製作方法,其係於前述基板上形成彩色濾光片,並於該彩色濾光片上塗佈前述樹脂組成物。
- 一種微透鏡之製作方法,其係將含有具有以下述式 (1)所表示之構造單位及以式(2)所表示之構造單位的共聚物、促進前述共聚物之硬化的觸媒以及溶劑之平坦化膜用或微透鏡用樹脂組成物塗佈於形成有彩色濾光片的基板上,並以高於100℃且將140℃設為上限之溫度進行烘烤而形成樹脂膜,於前述樹脂膜上形成阻劑圖型,將前述阻劑圖型進行回流而形成透鏡圖型,將前述透鏡圖型作為蝕刻遮罩來將前述樹脂膜進行回蝕,其中該促進前述共聚物之硬化的觸媒係選自由1,8-二氮雜雙環[5.4.0]十一烯-7及其之有機酸鹽、膦類、及鏻鹽所組成之群組,
(式中,R0各自獨立表示氫原子或甲基;R1表示單鍵或碳原子數1至5之伸烷基,該伸烷基亦可於其主鏈具有醚鍵;R2表示環氧基,或者具有環氧環之碳原子數5至12之有機基)。
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| JPH073116A (ja) * | 1993-06-18 | 1995-01-06 | Nippon Oil & Fats Co Ltd | 光硬化性樹脂組成物 |
| TW201310172A (zh) * | 2011-08-19 | 2013-03-01 | Fujifilm Corp | 正型感光性樹脂組成物、硬化膜的形成方法、硬化膜、液晶顯示裝置及有機el顯示裝置 |
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| JP2776810B2 (ja) | 1987-07-03 | 1998-07-16 | ソニー株式会社 | 固体撮像装置の製造方法 |
| JP2921770B2 (ja) | 1991-01-17 | 1999-07-19 | 日本化薬株式会社 | カラ−フィルター保護膜用樹脂組成物及びその硬化物 |
| JPH0675375A (ja) | 1992-08-26 | 1994-03-18 | Sony Corp | カラーレジスト材料 |
| JP3254759B2 (ja) | 1992-09-25 | 2002-02-12 | ソニー株式会社 | 光学素子およびオンチップレンズの製造方法 |
| US5380804A (en) * | 1993-01-27 | 1995-01-10 | Cytec Technology Corp. | 1,3,5-tris-(2-carboxyethyl) isocyanurate crosslinking agent for polyepoxide coatings |
| JP3381305B2 (ja) * | 1993-06-07 | 2003-02-24 | 東ソー株式会社 | マイクロレンズ用感光性組成物 |
| KR100642446B1 (ko) | 2004-10-15 | 2006-11-02 | 제일모직주식회사 | 열경화성 일액형 컬러필터용 보호막 조성물 및 이를이용한 컬러필터 |
| JP2008031417A (ja) | 2006-07-04 | 2008-02-14 | Jsr Corp | 熱硬化性樹脂組成物、保護膜および保護膜の形成方法 |
| JP5177418B2 (ja) * | 2008-12-12 | 2013-04-03 | 信越化学工業株式会社 | 反射防止膜形成材料、反射防止膜及びこれを用いたパターン形成方法 |
| JP2010237374A (ja) | 2009-03-31 | 2010-10-21 | Dainippon Printing Co Ltd | カラーフィルタ及び有機elディスプレイ |
| JP5950125B2 (ja) | 2011-07-07 | 2016-07-13 | 日産化学工業株式会社 | 樹脂組成物 |
| CN102955361B (zh) * | 2011-08-19 | 2018-04-06 | 富士胶片株式会社 | 正型感光性树脂组成物、硬化膜的形成方法、硬化膜、液晶显示装置及有机el显示装置 |
| JP5873450B2 (ja) | 2012-02-29 | 2016-03-01 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置及び有機el表示装置 |
| JP5692339B2 (ja) | 2013-11-25 | 2015-04-01 | 東洋インキScホールディングス株式会社 | 感光性組成物 |
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| JPH073116A (ja) * | 1993-06-18 | 1995-01-06 | Nippon Oil & Fats Co Ltd | 光硬化性樹脂組成物 |
| TW201310172A (zh) * | 2011-08-19 | 2013-03-01 | Fujifilm Corp | 正型感光性樹脂組成物、硬化膜的形成方法、硬化膜、液晶顯示裝置及有機el顯示裝置 |
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| KR20170041665A (ko) | 2017-04-17 |
| TW201609932A (zh) | 2016-03-16 |
| WO2016021348A1 (ja) | 2016-02-11 |
| US20170166737A1 (en) | 2017-06-15 |
| CN106663627A (zh) | 2017-05-10 |
| CN106663627B (zh) | 2020-06-09 |
| JPWO2016021348A1 (ja) | 2017-05-25 |
| US10487205B2 (en) | 2019-11-26 |
| JP6687906B2 (ja) | 2020-04-28 |
| KR102281050B1 (ko) | 2021-07-23 |
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