TW201140239A - Photosensitive resin composite and light-receiving device - Google Patents
Photosensitive resin composite and light-receiving device Download PDFInfo
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- TW201140239A TW201140239A TW100110287A TW100110287A TW201140239A TW 201140239 A TW201140239 A TW 201140239A TW 100110287 A TW100110287 A TW 100110287A TW 100110287 A TW100110287 A TW 100110287A TW 201140239 A TW201140239 A TW 201140239A
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- Prior art keywords
- resin composition
- photosensitive resin
- compound
- substrate
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- 239000000805 composite resin Substances 0.000 title abstract 3
- 229920005989 resin Polymers 0.000 claims abstract description 255
- 239000011347 resin Substances 0.000 claims abstract description 255
- 239000006096 absorbing agent Substances 0.000 claims abstract description 103
- 238000002834 transmittance Methods 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000011342 resin composition Substances 0.000 claims description 301
- 239000000758 substrate Substances 0.000 claims description 145
- 150000001875 compounds Chemical class 0.000 claims description 129
- -1 hydrazine compound Chemical class 0.000 claims description 97
- 229910000679 solder Inorganic materials 0.000 claims description 78
- 238000010521 absorption reaction Methods 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 41
- 125000006850 spacer group Chemical group 0.000 claims description 40
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- 239000002313 adhesive film Substances 0.000 claims description 36
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- 229920001187 thermosetting polymer Polymers 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- 239000002966 varnish Substances 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000005476 soldering Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- 239000004575 stone Substances 0.000 claims description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052732 germanium Inorganic materials 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
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- 125000000962 organic group Chemical group 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 206010036790 Productive cough Diseases 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
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- 150000002632 lipids Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- NWPRCRWQMGIBOT-UHFFFAOYSA-N 7-(2-hydroxyethyl)-1,3-dimethylpurine-2,6-dione Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CCO)C=N2 NWPRCRWQMGIBOT-UHFFFAOYSA-N 0.000 claims 1
- PUSHKFZARGFRAP-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)C(C#N)=C Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)C(C#N)=C PUSHKFZARGFRAP-UHFFFAOYSA-N 0.000 claims 1
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- 238000002835 absorbance Methods 0.000 abstract 2
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- 238000010438 heat treatment Methods 0.000 description 18
- 239000004065 semiconductor Substances 0.000 description 17
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- 125000000217 alkyl group Chemical group 0.000 description 14
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 7
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
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Classifications
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- Solid State Image Pick-Up Elements (AREA)
Description
201140239 六、發明說明: 【發明所屬之技術領域】 本發明係關於經由對準步驟所製造的半導體裝置,特別係 關於用於製造搭載了 CMOS影像感測器之受光裝置的抗焊 用感光性樹脂組成物、及使用其所製造的受光裝置。 【先前技術】 影像感測器係將光學映像轉變為電子信號的半導體裝 置。作為此種影像感測器,有如CCD影像感測器與CM〇s 影像感測器。 習知以來,作為數位相機等之攝影元件,係使用CCD影 像感測器。然而’相較於CCD影像感測器,CM〇s影像感 測器因消耗電力較少、可小型化,故開始被採用。 該CMOS影像感測器係形成於石夕基板上,由受光元件、 彩色濾光器、微透鏡等所構成。 搭載著CMOS影像感測器之受先裝置的習知形態,如 電路基板上搭載C:順料❹⑼,c廳料感測& 絲與電路基板係藉由打線接合予以連接。此種打線接合; 式之⑽S影像感測器搭載受光裝置,由於需要 打線的空間’故裝置整體變大。 因此,近年來開發出晶片尺寸的受光裝置 CMOS影像感測器所搭載切基板上設 ^在“ 孔,藉由於該通孔内面所形成 ;貝、孔的ΐί 成之佈線電路,使形成於石夕基本 100110287 4 201140239 上面之佈線電路、與形成於矽基板下面之佈線電路連接,矽 基板下面之佈線電路與電路基板藉由焊接所連接。 作為此種晶片尺寸之CMOS影像感測器搭載受光裝置, 可舉例如曰本專利特開2007_67〇n號公報(專利文獻丨)。特 開2007-67017號公報(專利文獻1)中記載有下述半導體裝置 之製造方法。根據該製造方法,首先,於半導體元件之一面 侧的電極墊及裝置形成層之表面上形成第丨抗蝕層。接著, 於電極墊上藉钮刻形成開口。其次,於基板上藉姓刻形成一 端連通至開口、另一端在半導體元件之另一面側開口的貫通 孔。接著,於貫通孔形成貫通電極。進而,亦揭示有藉上述 製造法所製造之受光裝置。 另外,曰本專利特開2007-73958號公報(專利文獻2)中, 記載有下述影像感測器模組用晶圓等級晶片尺寸的封裝製 造方法。根據其製造方法,Α)將影像感測器晶圓與玻璃晶圓 黏合後,於影像感測器晶圓形成貫通孔。接著,Β)以導電物 夤填充形成於影像感測器晶圓的貫通孔,藉此形成導電體。 接著,C)於導電體末端形成銲錫凸塊,並與形成了電路的 PCB基板連結。進而,揭示有藉上述製造方法所製造的受 光裝置。又,特開2007-73958號公報(專利文獻2)中,亦揭 示了玻璃晶圓被IR截止濾波層所塗敷。 專利文獻1 :日本專利特開2007-67017號公報 專利文獻2:曰本專利特開2007-73958號公報 100110287 5 201140239 【發明内容】 (發明所欲解決之問題) 本發明者等人,針對此種晶片尺寸之CMOS影像感測器 搭載受光裝置進行重複研究,結果發現’因由矽基板下側面 穿透抗焊劑而進入的紅外線,將引起感測器晶片(受光元件) 的誤作動。 因此,本發明者等人為了遮阻由矽基板下面側進入的紅外 線’而嘗試在抗焊劑表面進一步形成遮光膜。 然而’藉由此種手法,雖然可遮阻由石夕基板下面側所進入 的紅外線,但產生為了形成遮光膜而製造成本上昇、以及遮 光膜之形成步驟造成額外負擔的問題。 (解決問題之手段) 根據本發明,提供一種感光性樹脂組成物’其特徵為含有: 鹼可溶性樹脂(A); 光聚合起始劑(B);與 最大吸收波長為800nm以上且2500nm以下之範圍内的紅 外線吸收劑(D); 波長400nm以上且700nm以下之可見光穿透率的最大值 為5.0%以上。 另外,根據本發明,提供一種感光性樹脂組成物’其特徵 為含有: 鹼可溶性樹脂(A); 100110287 201140239 光酸產生劑(c);與 敢大吸收波長為800nm以上且2500nm以下之範圍内的紅 * 外線吸收劑(D); 波長400nm以上且700nm以下之可見光穿透率的最大值 為5.0%以上。 另外’根據本發明,提供一種受光裝置,其特徵為,屬於 下述之CMOS影像感測器搭載受光裝置;其係具有: 搭載著由光元件所構成之CMOS影像感測器之矽基板; 透明基板;與 規定上述CMOS影像感測器與上述透明基板之間之間隙 的間隔件; 上述矽基板係設有通孔; 藉由形成於上述通孔内面之佈線電路’使上述矽基板上面 之佈線電路與上述矽基板下面之佈線電路連接; 於上述矽基板下面係設有抗銲層; 使上述矽基板下面之佈線電路、與電路基板之佈線電路藉 銲接而連接; ' 上述抗銲層係上述任一之感光性樹脂組成物的硬化物。 • 根據本發明’本發明之感光性樹脂組成物係含有最大吸收 波長為800nm以上且2500nm以下之範圍内的紅外線吸收劑 (D)’波長400nm以上且700nm以下之可見光穿透率的最大 值為5.0%以上。設有屬於此感光性樹脂組成物之硬化物之 100110287 7 201140239 抗銲層的CMOS影像感測器搭載受光裝置中,感光性樹脂 組成物含有紅外線吸收劑。藉此,可防止紅外線由矽基板下 面側進入。又,本發明之感光性樹脂組成物係具有可見光穿 透性。藉此,在上述受光裝置之製造步驟的對準時,可辨識 印字於矽基板下面之對準記號。 如此,感光性樹脂組成物可穿透可見光,且感光性樹脂組 成物之硬化物可遮阻紅外線。因此,可提供具有尤其是耐熱 性、耐藥品性、耐濕性、低曲翹性等之抗銲層所需性能的抗 銲層用之感光性樹脂組成物。 (發明效果) 根據本發明,感光性樹脂組成物可穿透可見光,且感光性 樹脂組成物之硬化物可遮阻紅外線。因此,可提供具有尤其 是耐熱性、耐藥品性、耐濕性、低曲翹性等之抗銲層所需性 能的抗銲層用之感光性樹脂組成物。 【實施方式】 藉以下所述之較佳實施形態及其隨附之圖式進一步闡明 上述目的及其他目的、特徵及優點。 本發明之第一形態的感光性樹脂組成物(以下亦記載為本 發明之感光性樹脂組成物(1))’其特徵為含有驗可溶性樹脂 (A)、光聚合起始劑(B)與最大吸收波長為800nm以上且 25〇〇nm以下之範圍内的紅外線吸收劑(d),且波長400nm 以上且700nm以下之可見光穿透率的最大值為5.0%以上。 100110287 8 201140239 本發明之感光性樹脂組成物(1)係負型感光性樹脂組成物, 為半導體裝置之抗銲層用感光性樹脂組成物。 • 本發明之第二形態的感光性樹脂組成物(以下亦記載為本 • 發明之感光性樹脂組成物(2)),其特徵為含有鹼可溶性樹脂 (A)、光酸產生劑(C)與最大吸收波長為800nm以上且 2500nm以下之範圍内的紅外線吸收劑(D),且波長400nm 以上且7〇〇nm以下之可見光穿透率的最大值為5.0%以上。 本發明之感光性樹脂組成物(2)為負型之感光性樹脂組成 物,為半導體裝置之抗銲層用感光性樹脂組成物。 如圖1所示’本發明之感光性樹脂組成物(1)及本發明之 感光性樹脂組成物(2),係用於製造晶片尺寸之CMOS影像 感測器搭載受光裝置的感光性樹脂組成物。又,本發明之感 光性樹脂組成物(1)及本發明之感光性樹脂組成物(2)係在藉 曝光及驗顯影而圖案化後,藉由進行熱硬化,而用於形成抗 焊層。 尚且’以下說明中’本發明之感光性樹脂組成物(1)及本 發明之感光性樹脂組成物(2) ’係以用於形成晶片尺寸之 • CMOS影像感測器搭載受光裝置之抗鮮層的使用形態例作 為本發明之使用形態例而進行說明。然而,本發明之感光性 樹脂組成物(1)及本發明之感光性樹脂組成物(2)並不限於晶 片尺寸之CMOS影像感測器搭載受光裝置的製造用。此等 亦可用於形成例如經由藉對準步驟、曝光、顯影而圖案化之 100110287 9 201140239 步驟所形成,且具有遮阻紅外線之機能的保護膜。此等尤其 適合用於半導體裝置之抗銲層形成。 參照圖1,說明使用本發明之感光性樹脂組成物(1)及本發 明之感光性樹脂組成物(2)而製造的晶片尺寸之CMOS影像 感測器搭載受光裝置1。圖1為晶片尺寸之CMOS影像感測 器搭載受光裝置的概略剖面圖。圖1中,受光裝置1具有石夕 基板6與透明基板3。於矽基板6上面11上形成有受光部8。 而且,在形成於矽基板6上面11之受光部8與透明基板3 之間,設有間隔件4以形成間隙5。藉此間隔件4,規定受 光部8(矽基板6)與透明基板3之間的間隙5。又,受光裝置 1係藉由於電路基板2上依銲錫9進行銲接而搭载。 此受光部8亦即為CM0S影像感測器。又,受光部8主 要由形成於矽基板6上之受光元件(未圖示)所構成。除了受 光部8(CM〇S影像感測器)以外,尚具有:在♦基板6上面 11 ^受光元件之周圍所形成的佈線電路;形成於受光元件 及受光元件周圍的佈線電路上所形成的作為絕緣膜的層間 絕緣膜(未圖示);彩色濾、光器(未圖示);微透鏡(未圖示曰); 或連接佈線電路的電極墊(未圖示)等。 裝置1切基板6上’設有屬於貫通孔的通孔 在石夕基板6上面u、祕1〇内面及石夕基板6下面η, 有佈線電路。χ,藉由形成於通孔1()内面之佈線電路 @基板6上面u之佈線電路、與下面12之佈線電路讀 100110287 201140239 而且,電路基板2之佈線電路、與矽基板6下面12之佈線 電路(22 ’參照圖16等)係經由銲錫9所連接。 電路基板2係於將銅箔等經蝕刻加工的電路圖案上,形成 鍍敷了錄、金專之佈線電路的基板。電路基板2之材質並無 特別限定,有如於玻璃纖維中浸含了樹脂的有機基板、陶瓷 基板、鋁、銅等之金屬基板等。又,電路基板2可為單層之 電路基板’亦可為多層之電路基板。 透明基板3為玻璃基板或丙稀酸、聚碳酸酯、聚驗;g風等之 有機基板。透明基板3係依與受光部8之間隔著間隙5、並 與文光部8相對向之方式,經由間隔件4而設置於受光部$ 上方。 間隔件4係為了在透明基板3與受光部8(CM〇s影像残 測器)之間確保空間,而用於在受光部8與透明基板3之間 形成間隙5者。 矽基板6上面11,形成有受光部8、亦即CM〇s影像感 測器。又,於矽基板6下面12,形成有佈線電路(22)。又, 矽基板6上設有通孔1〇。藉此,經由形成於通孔1〇内面的 佈線電路,使矽基板6上面U之佈線電路(15)與下面12之 佈線電路(22)連接。 而且,矽基板6下面12之佈線電路(22)中,除了銲錫連 接部以外,係被覆有屬於絕緣層之抗銲層(25)。又,於銲接 部分上配置有銲錫9。 100110287 11 201140239 抗銲層(25)在銲接時,可僅有搭載著銲錫9之部分被連接 於下面12之佈線電路(22),而絕緣部分未予以連接。又, 抗銲層(25)可保護矽基板6下面12及矽晶圓6下面12之佈 線電路(22)的非連接部分。 連接於矽基板6下面12之佈線電路(22)的銲錫9未被覆 抗銲層(25)。藉此,使該銲錫9與電路基板2上之佈線電路 連接。 接著,參照圖2〜圖16,說明使用本發明之感光性樹脂組 成物(1)或本發明之感光性樹脂組成物(2)之晶片尺寸的 CMOS影像感測器搭載受光裝置的製造步驟。圖2〜圖 表示晶片尺寸之CMOS影像感測器搭載受光裝置之製造氺 驟的概略剖面圖。又,圖2〜圖16係於晶片尺寸之 影像感測器搭載受光裝置中,放大了設置通孔之附攻的圖 因此,並未顯示出晶片尺寸之CMOS影像感測器搭栽灸“ 裝置的整體。 乂光 首先,如圖2所示’在矽基板6上面11形成由受光元件(未 圖不)、形成於受光元件周圍之佈線電路15、絕緣祺Ο、
色濾光器(未圖示)、微透鏡(未圖示)、電極墊16等所樽戍的 文光部8。藉此,製作於矽基板6上搭載著受光部8的 影像感測器搭載矽基板4〇。又,於圖2,受光部8 S 不佈、本電路15、絕緣膜17及電極墊16。作為絕緣辑17 ‘ 無特別限制,可舉例如siN、Si〇2等之無機材料、、^ 100110287 201140239 樹脂、聚笨并十坐樹脂、苯并環丁稀樹脂等之有機材料。 接著,如圖3所示,以被覆受光部8上面整體的方式(圖 2所不部分中,係以被覆絕緣膜17及電極塾μ之方式), 於又光。p 8上形成間隔件用感光性樹脂組成物層如。間隔 件用感紐樹脂組成物層4a係與抗銲㈣感光性樹脂組成 物不同’為㈣隔件狀感光性樹脂組成物所構^將間隔 件用之感光性樹脂組成物於受光部8上形成為層狀後,藉由 曝光及顯影而圖案化為間隔件4之形狀。作為此種間隔件用 感光性樹脂組成物並無特別限制,若為可藉上述步驟而圖案 化為間隔件4之形狀者即可。又,間隔件用感光性樹脂組成 物可為負型或正型。又,間隔件用感紐樹驗成物於饥 下可為液狀或薄膜狀。在間隔件用感光性樹脂組成物於 沉下呈液狀的情況,可藉旋塗、印刷等手法,形成間隔件 == 脂'嶋層4a。又,在間隔件用感光性樹脂組 成物於25C下呈薄膜壯沾比 潯膜狀的情況,可藉層合等手法形成 件用感光性樹脂組成物層知。
·所不,在間隔件用感光性樹脂組成物層4a - 上側配置遮罩33。女,料A /、人對未被遮罩33所遮蔽之部分的間 .隔件用感光性樹脂組成物層4a||紫外線34進行曝光。又, 在間隔件用感光性樹脂組成物為負型的情況,係對間隙5 所幵乂成P刀進订遮罩,對間隔件4所形成之部分照射曝光 " φ在間隔件用感光性樹脂組成物為正型的情 100110287 13 201140239 況,係對間隔件4所形成 之部分照射曝光光。曝間隙5所形成 無特別限制,可使用,為紫外線’作為曝光光之光源並 接著,如圖5所亍Y線、1射線、激分子雷射等光源。 物層-藉顯影液崎=曝光之間隔件用感光性樹脂組成 組成物為負型的产'於此’在間隔件用感光性樹脂 分)去除。另/面兄將未曝光部分(間隙5所形成之部 的情況,係將曝先件用感光㈣地組成物為正型 在受光部8切^隙5卿成之部分)去除。藉此, 樹脂組成物4a。亦g K 圖案化為_件形狀的間隔件感胃光性 包圍石夕基板6上之L’、在俯視時(由圖5之上側觀看時),依 式,形成間隔件用二光疋件、彩色濾光器、微透鏡等之方 用感光性樹脂植成物心 隔件用感光性樹脂組' 。此經圖案化之間 光部8與透明基拓 4a係於其後之步驟,成為在受 板3接黏的間成 舉例如溶劑、鹼嘩I势 …”、办液並無特別限制,可 顯影液。〜其中,較佳為姆環境負擔少的驗 其次,如圖6所-_ 將受光部8與物 4由形成於X光部8上之間隔件4, 黏方法並無特別^板3接黏。受光部8與透明基板3之接 先,進行受切 舉例^述㈣赖㈣方法。首 接著,藉由押印^载之%基板6與透明基板3之定位。 __ 毒材之押印面,由,6侧或透明基板3 201140239 側進行加熱及加壓。如μ 精由間隔件4,將受光部8與透 明基板3接黏,而得到 土板6及透明基板3的接合體35。 /、-人,如圖7戶斤示,藓妒斗紅+丨缺 稭乾式蝕刻等,於接合體35之矽美 板6上形成屬於貫通孔的 ▽逋孔18。此時,將通孔18形成至 到達電極墊16為止。 接著’如圖8所示,在诵丨 仳逋孔18内面及矽基板6下面12 之整體,藉CVD(化學蒗 ^ 、、锻)寻形成Si〇2等之絕緣膜19。 接著如圖9所不,藉乾式姓刻等’將形成於電極塾16 上之絕_19去除,使電極墊16露出。 其次’如圖ίο所示’在通孔18内面及石夕基板6下面12 之、’、邑緣膜19上’域成為鍍銅基底的阻蔽層。作為阻蔽 層20並無特別限制,可舉例如Ή、Ti/cu、&、见、c遲 等。 接著如圖11所不,在阻蔽層20上,藉無電解鍍敷法、 電鍍法等形成鍍銅層21。 其次’如® 12所示’將阻蔽層及鍍銅層21侧成石夕基板 6下面12之佈線電路圖案,而形成銅佈線電路22。 接著,如圖13所示,於通孔18内部填充本發明之感光性 樹脂組成物(1)或本發明之感光性樹脂組成物(2),同時以本 發明之感光性樹脂組成物(1)或本發明之感光性樹脂組成物 (2)被覆亦包括銅佈線電路22所形成之部分的矽基板6下面 12侧的整體。藉此,形成本發明之感光性樹脂組成物層23。 100110287 15 201140239 作為本發明之感光性樹脂組成物層23的形成方法並無特別 限制,可舉例如以下方法。首先,使矽基板6下面12側朝 上,將溶解或分散於溶媒之本發明之感光性樹脂組成物(1) 或本發明之感光性樹脂組成物(2)塗佈於矽基板6下面12。 其次,使溶媒揮發去除。又,作為其他方法,可為以下方法。 首先,製作糊狀之本發明之感光性樹脂組成物(1)或本發明 之感光性樹脂組成物(2)。接著,使矽基板6下面12朝上, 塗佈於梦基板6下面12側。又,作為其他方法,亦可將形 成於知片材上之薄膜狀的本發明之感光性樹脂組成物⑴ 或本發明之感光性樹脂組成物(2)(接黏薄膜),壓黏於石夕基板 6下面12側的方法等。 其次,如圖14所示,於本發明之感光性樹脂組成物層23 中’依可僅將對應至銲球搭載部分26之部分去除的方式設 置遮罩並照射曝光光。接著,以_影液等進行顯影,而將 =於銲球搭載料之部分的本㈣1紐難組成物 ()或本發明之感光性樹脂組成物⑺去除。如此,對本發明 之感先性樹脂組成物層23進行圖㈣,使形成㈣基板6 佈線電路22心。又,•本判之感光性 ==)為負型,故對形成銲輯部分之部分設置 遮罩,而對㈣抗銲層之部分照㈣光光。另 =感光性樹脂組成物(2)為正型,故對形一 4刀進成銲球搭嶋之部分照射曝光光。 100110287 16 201140239 曝光光為紫外線,作為曝総之光源並無特觀制,可使用 g射線、i射線、激分子雷射等光源。 此曝光時,為了在矽基板6下面12側之必要位置上形成 經圖案化之本發明的感光性樹脂組成物層24,而必須在感 光性樹脂組成物層23之曝光前進行遮罩之定位(對準)。此 對準係藉由使事先配置於矽基板6下面12之對準記號、與 遮罩之對準記號—致而進行.此時,在矽基板6下面I】側 係形成有本發明之感光性樹脂組成物層23。因此,對準時, 通過本發明之感光性樹脂組成物層23而辨識矽基板6下面 12之對準記號。此步驟巾’由於本發明之感光性樹脂組成 物⑴及本發明之感光性樹脂組成物⑺具有使可見光穿透的 性質,故可確實地辨識對準記號。 接著’如® 15所示,象經圖案化之本發明之感光性樹脂 組成物層24進行加熱使其熱硬化。藉此,形成抗銲層25。 接著於圖15巾之;^基板6下面12側之銲球搭載部分 搭載銲球27。藉此,如圖16所示般得到搭載了鲜球 之CMOS影像感測器搭載受光裝置(受光裝置”。 " 圖、图16中,間隔件4雖例示為形成於受光部8 之升八、i_並不限定於此,間隔件4亦可直接形成於石夕基 板6之表面上。 尚且,如圖17戶斤; 叮不’搭載了銲球27之CMOS影像感測 器搭載受光裝置(受以置υ亦可不為1個丨個製作者。例 100110287 201140239 如,使用1片大型矽基板6進 置1於平面方向上相連者3〇( ^使多數之受光裝 圖π之左右方向及紙面之表背面方平;;方向係指圖17中, 裝置1於平面方向上相連者 Μ’將多數受光 所示位置上進行各個受光裝置;^17所錢,在符號η 到晶片尺寸之⑽影像㈣=化(_),藉此可得 ”。作為切割方法並無特_二舉=;= 2明基板3側切人至間隔件4_基板6之界面。接著, 藉由由矽基板6下側切入而予以切割。 -進仃CMOS景;像感測器搭载受光裝置之發基板6 下面12側所搭載之銲球27 '與經由銲球π而連接之電路 基板上之佈線電路較位。接著進行加熱,而予以銲接。藉 此,將CMOS影像感測器搭载受光裝置搭載於電路基板: (例如圖1中之電路錢2上)。進行銲接之歸並無特別限 制’可藉迴銲裝置進行。 如上述般所製造之受光裝置1係具有下述特徵。如圖16 所示般,在石夕基板6下面(12)側,鮮接後,鋒球27或銅佈 線電路22所存在之部分係藉由銲球η或銅佈線電路^, 而遮阻由絲板6下面12側進人的紅外線。又,不存在銲 球27及銅佈線電路22的部分,係如後述般藉由含有紅外線 吸收劑(D)的抗銲層25,而遮阻㈣基板6下面⑽側進入 的紅外線。如此,使用本發明之感光性樹脂組成物(1)或本 100110287 18 201140239 發明之感光性樹脂組成物(2)所製造的受光裝置丨,紅外線不 致由矽基板6下面(12)側進入。 其次,針對用於形成上述受光裝置1之抗輝層25之本發 明之感光性樹脂組成物(1)及本發明之感光性樹脂組成物 (2) ’進行詳細說明。本發明之感光性樹脂組成物(丨)及本發 明之感光性樹脂組成物(2)係硬化前之感光性樹脂組成物具 有可見光穿透性。藉此,於對準時,可辨識印字於矽基板下 面之對準記號。又,本發明之感光性樹脂組成物(1)及本發 明之感光性樹脂組成物(2),係於感光性樹脂組成物之硬化 後可防止紅外線由石夕基板下面側進入。又,本發明之感光 性樹脂組成物(1)及本發明之感光性樹脂組成物(2)係感光性 树月曰組成物之硬化物具有抗銲層所需之性能,亦即具有耐熱 性 '耐藥品性、絕緣性、耐濕性、低曲翹性、對準性。 本發明之感光性樹脂組成物(1)係藉由曝光及鹼顯影,使 曝光部分殘存,並去除祕光部分的負型之感光性樹脂組成 物本發明之感光性樹脂組成物⑴含有鹼可溶性樹脂⑷、 光聚合起始劑⑼與最大吸收波長為_mn以上且250〇nm 以下之範圍内的紅外線吸收劑(D)。 本毛明之感光性樹脂組成物⑴由於為負型之感光性樹脂 組=,故屬於藉由照射曝光光而進行聚合的光聚合性感光 !· Μ月u成物’且在藉曝光光之照射及驗顯影而進行了圖案 化後藉加熱進仃熱硬化而成為熱硬化物的樹脂組成物。因 100110287 19 201140239 此,作為本發明之感光性樹脂組成物⑴,可舉例如以下形 態例。 ⑴含有具有Μ合性雙鍵且具有驗可溶性基之驗可溶性 樹脂(Α-2)、光聚合起始劑⑻與紅外線吸收劑⑼的感光性樹 脂組成物。 (H)含有不具有光聚合性雙鍵且具有驗可溶性基之驗可溶 性樹脂⑹)、具有光聚合性雙鍵且具有驗可溶性基之驗可 溶性樹脂(Α·2)、光聚合起始劑(β)與紅外線讀_)的感光 性樹脂組成物。 σπ)含有不具有光聚合性雙鍵且具有驗可溶性基之鹼可 溶性樹脂⑹)、光聚合起始_)、紅外線吸收·)與光聚 合性化合物(G)的感光性樹脂組成物。 σν)含有具有光聚合性雙鍵且具有驗可溶性基之驗可溶 性樹脂(Α-2)、光聚合起始劑⑻、紅外線吸收劑⑼與光聚合 性化合物(G)的感光性樹脂組成物。 (V)含有*具有光聚合性雙鍵且具有驗可溶性基之驗可溶 性樹脂(Α-1)、具有光聚合性雙鍵且具有驗可溶性基之驗可 溶性樹脂(Α-2)、光聚合起始劑(Β)、紅外線吸收劑(d)與光聚 合性化合物(G)的感光性樹脂組成物。 本發明之感光性樹脂組成物⑴中,驗可溶性樹脂(a)係在 曝光後藉驗顯影液被顯影時,未曝光部分溶解於驗顯影液中 而被去除。如此,本發明之感光性樹脂組成物⑴因為含有 100110287 20 201140239 鹼可溶性樹脂(A),故可藉曝光光照射選擇性地進行圖案 化。曝光光為紫外線,較佳為3 60nm以上且4〇〇nm以下的 紫外線。作為曝光光之光源並無特別限制,可使用g線、i 線、激分子雷射等光源。 本發明之感光性树知組成物(1)的驗可溶性樹脂(A),為對 驗顯影液呈稽性的樹脂’料子内具有鹼可溶性基。驗可 溶性基為酚性羥基(鍵結於芳香族環之羥基)或羧基。又,鹼 可溶性樹脂(A)係為了使顯影後之_案化的感光性樹脂組 成物層被熱硬化,而具有酚性羥基、醇性羥基、羧基、酸酐 基、胺基、氰酸酯基等之藉加熱而進行熱硬化反應的熱反應 基。 本發明之感光性樹脂組成物(1)中的鹼可溶性樹脂(A),有 如不具有光聚合性雙鍵且具有驗可溶性基之驗可溶性樹脂 (A-1)、熟有歧合性雙鍵且射驗可溶縣讀可溶性 樹脂(Α·2)。該絲合性雙鍵係域由曝光光照射,而與其 他分子之光聚合性雙鍵進行聚合反應的基。例如乙烤基、(甲 基)丙稀基、烯丙基等之取代基巾之魏、或分子鏈中之雙 鍵。 作為驗可雜樹脂(U),可舉例如甲㈣、紛型、雙紛 A5L又紛F型、鄰苯二酉分型、間苯二紛型、五倍子紛型等 之祕清漆樹脂,雜基樹脂、參苯基甲烧㈣樹脂、聯 苯基芳烧基型_脂、α•祕芳烧基型賴脂、卜萘紛芳烧 100110287 21 201140239 基i Μ月曰經基本乙烯樹脂、曱基丙稀酸樹脂、丙晞酸樹脂、 含有羥基、羧基等之環狀烯烴系樹脂,聚醯胺系樹脂(具體 而=,係具有聚苯并β号唾構造及聚醯亞胺構造之至少一者, 且於主鏈或側鏈上具有羥基、羧基、醚基或酯基的樹脂,具 有聚苯并哼唑前驅物構造之樹脂,具有聚醯亞胺前驅物構造 之樹脂,具有聚醯胺酸酯構造之樹脂等)等。此等樹脂係於 分子内具有屬於鹼可溶性基之酚性羥基或羧基。又,鹼可溶 性樹脂(Α-1)中亦包括:曱酚、雙酚Α、雙酚F、鄰苯二酚、 間苯二酚、五倍子酚等之重複單位數為丨個的低分子量化合 物,或曱酚型、酚型、雙酚A型、雙酚F型、鄰笨二酚型、 間苯二酚型、五倍子酚型等之酚醛清漆樹脂等之重複單位數 為2個以上的高分子量化合物。 另外,本發明之感光性樹脂組成物(丨),亦可含有含敌基 之丙烯酸樹脂般之鹼可溶性熱可塑性樹脂。 作為鹼可溶性樹脂(A-2) ’可舉例如於鹼可溶性樹脂 般之具有鹼可溶性基的樹脂中導入了具有雙鍵之基的樹 脂;於具有光聚合性雙鍵之樹脂中導入了鹼可溶性基之樹脂 等。又,本發明中’(曱基)丙烯酸基係指丙烯酸基或曱基丙 烯酸基,又’(甲基)丙烯醯基係指丙烯醯基或曱基丙烯醯基。 鹼可溶性樹脂(A-2)中,作為於鹼可溶性樹脂(A—〗)等般之 具有鹼可溶性基的樹脂中導入了具有雙鍵之基的樹脂,可舉 例如於酚樹脂之酚性羥基一部分使環氧丙基(曱基)丙烯酸 100110287 22 201140239 酯反應而得的(甲基)丙烯酸改質酚樹脂,或使雙酚A等之雙 酚化合物之一方的羥基與環氧丙基(甲基)丙烯酸酯反應而 • 得的(甲基)丙烯酸改質雙酚等。又,作為於具有光聚合性雙 鍵之樹脂中導入了鹼可溶性基的樹脂,可舉例如:於雙酚化 合物之兩方的羧基,使具有(甲基)丙烯酸基與環氧基之化合 物’例如對於使環氧丙基(甲基)丙婦酸酿之環氧基反應而得 之樹脂的絲,使_反應,而導人了縣的樹脂;於雙驗 化合物之兩方的經基具有(甲基)丙烯酸基與環氧基的化合 物/列如對於使環氧丙基(甲基)丙烯酸醋之環氧基反應而得 之樹脂的絲,使二㈣反應,而導人了躲的樹脂等。 驗可溶性樹脂(A)t,較佳祕可溶性細旨(a_2),特佳為 (曱基)丙烯酸改質酚樹脂。 藉由使用驗可溶性樹脂(A_2),曝光時可使曝光部確實進 打交聯。藉此可於顯影時防止曝光部溶解於顯影液。又, 可提升曝光後之曝光部的機械強度。如此,可提升形狀保持 /性树脂(A-2)中,在對於鹼可溶性樹脂 等般之具有驗可溶性基之樹脂陳可溶性基上,導入了 又鍵之基的_日的情況’驗可溶性基當量(分子量/驗可溶性 基之數)並無特別限定,較佳為%以上且2_以下 為-以上且_以下。驗可溶性基當量若大於上限值:: 驗顯影性降低,有顯影需要長時間的情況。又,糾、於下限 100110287 23 201140239 值’則有曝光部之彡魏降低的情況。又,驗可溶性基 當量係以分子量計而使用重量平均分子量所算出。 另外’驗可洛性樹脂(A_2)中,在對於使雙盼化合物之兩 方之羥基與具有(曱基)丙烯酸基與環氧基之化合物的環氧 基反應而得到之樹脂_基,使酸酐或二舰反應, 而導入 了叛基的樹脂的情況,驗可溶性基當量(分子量/驗可溶性基 之數)並無制限定,較佳為3Q以上且2_以下,特佳為 50以上且1〇〇〇以下。该驗可溶性基當量若大於上限值,則 驗顯影性降低,有顯料要長時_情況。又,若小於下限 值’則有曝光部之賴影耐性降低的情況。 本發明之感光性樹脂組成物⑴係進行曝光光之照射及驗 顯影’經圖案化後’進行力4以熱硬化,藉此成為半導 體裝置之抗録層#之保護膜。然後,本發明之感光性樹脂組 成物(1)視藉由加熱而進行熱硬化時之作用,而鹼可溶性樹 脂(A-1)有以下2種樹脂: (1)藉由與環氧樹脂等之熱硬化性樹脂進行反應而形成硬 化物的熱硬化性樹脂加成型之樹脂 — " ~ -- -- ... (ii)藉由鍵結於本身之分子鏈上的官能基於分子鏈内進行 環化反應而形成硬化物的自己縮合型之樹脂 尚且,在⑴熱硬化性樹脂加成型之樹脂的情況,本發明之 感光性樹脂組成物(1)係含有與(i)熱硬化性樹脂加成型之樹 脂進行熱硬化反應的熱硬化性樹脂。又,在(丨丨)自己縮合型 100110287 24 201140239 之樹脂的情況,本發明之感光性樹脂組成物(ι)可人 石 化性樹脂,亦可不含。 D a有熱硬 j 驗可溶性義(Α·1Η,作為_魏性㈣旨加成型之樹 月曰,可舉例如酚酚醛清漆樹脂、聚醯胺酸等,更具體可舉例 如甲酚型、酚型、雙酚Α型、雙酚F型、鄰笨二酚型、間 苯二紛型、五倍子之祕清漆樹脂,盼芳絲樹脂、 羥基苯乙烯樹脂、甲基丙烯酸樹脂或甲基丙烯酸酯樹脂等之 丙烯酸系樹脂,含有羥基、羧基等之環狀烯烴系樹脂。 另外’鹼可溶性樹脂(A_1)t,作為(ii)自己縮合型之樹脂, 有如聚醯胺系樹脂,更具體可舉例如:具有聚苯并嘮唑構造 及聚醯亞胺構造之至少一者,且於主鏈或側鏈上具有羥基、 羧基、醚基或酯基的樹脂,具有聚苯并噚唑前驅物構造之樹 脂,具有聚醯亞胺前驅物構造之樹脂,具有聚醯胺酸酯構造 之樹脂等。 本發明之感光性樹脂組成物(1)係視藉加熱進行熱硬化時 之作用,而鹼可溶性樹脂(A_2)有以下2種之樹脂: (1)藉由與環氧樹脂等之熱硬化性樹脂進行反應而形成硬 化物的熱硬化性樹脂加成型之樹脂 (ii)藉由鍵結於本身分子鏈上之官能基於分子键内進行環 化反應而形成硬化物的自己縮合型之樹脂。 又’在⑴熱硬化性樹脂加成型之樹脂的情況,本發明之感 光性樹爿B組成物(1)係含有與⑴熱硬化性樹脂加成型之樹脂 100110287 25 201140239 進行熱硬化反應的熱硬化性樹脂。又,在n 自己縮合型之 樹脂的情況,本發明之感光性樹脂組成物(1)可含有熱硬化 性樹脂,亦可不含。 鹼可溶性樹脂(A-2)中,作為⑴熱硬化性樹脂加成型之樹 脂,可舉例如對於使(甲基)丙烯酸改質酚樹脂、(甲基)丙烯 酸改質雙*、雙紛化合物之兩方的經基與具有(曱基)丙稀酸 基與環氧基之化合物反應而得之樹脂的羥基,使酸酐反應, 而導入了羧基的樹脂;對於使雙酚化合物之兩方之羥基與具 有(甲基)丙烯酸基與環氧基之化合物反應而得之樹脂的羥 基’使二羧酸反應’而導入了羧基之樹脂等。 另外,驗可溶性樹脂(A-2)中,作為(ϋ)自己縮合型之樹脂, 有如於聚醯胺系樹脂中導入了(甲基)丙烯酸基的樹脂,更異 體可舉例如:對於具有聚苯并η等唑構造及聚醯亞胺構造之多 少一者,且於主鏈或侧鏈上具有羥基、羧基、醚基或酯基的 樹脂、具有聚苯并呤唑前驅物構造之樹脂、具有聚醯变胺前 驅物構造之樹脂、具有聚酿胺酸酯構造之樹脂等,導入了(甲 基)丙烯酸基的樹脂等。 尚且,鹼可溶性樹脂(Α·2)中之光反應性的雙鍵,係在# 光光照射時’大部分會進行光聚合,但有時其中一部分係在 曝光光之照射時’不進彳于光聚合而殘存。此種於曝光光热射 時未進行光聚合的雙鍵’係在熱硬化時進行熱聚合。 鹼可溶性樹脂(Α)之重量平均分子量並無特別限定,較值 100110287 26 201140239 為300,000以下’特佳為5 〇〇〇以上且15〇,〇〇〇以下。若驗 可溶性樹脂(A)之重量平均分子量為上述範圍,則形成間隔 件4時之製膜性特別優越。於此,重量平均分子量係使用例 如GPC(凝膠滲透層析)所評價,藉由預先使用苯乙稀標準物 質所作成的標準線算出重量平均分子量。又,使用四氫吱喃 (THF)作為献溶媒,於赋之溫度條件下崎測定。 本發明之感光性樹脂組成物⑴中之驗可溶性樹脂⑷的 含量並無特別限定,在本發明之感光性樹脂組成物⑴不含 後述之無機填充材的情泥,本發明之感光性樹脂組成物⑴ 中之鹼可溶性樹脂⑷的含量為10重量%以上且80重量% 以下,較佳15重量%以上且7〇重量%以下。另一方面在 本發明之感光性樹脂組成物⑴含有後述之無機填充材的情 二光性樹脂組成物⑴中之驗可溶性樹脂㈧的 a里係相對於由本發明之感光性樹脂組成 填充劑之成分的合計,較佳為15 “機 下、特佳20重量%以上且5〇番旦 60重量%以 ㈧之含+、 以下。若驗可溶性樹脂 /述下限值,則有於曝光、顯 性樹脂組絲之殘㈣情形。又,若超過上述上限值 於曝光、顯影時形成圖宰 、 大,而發生圖案厚度偏差的情況。 〜支 有光性樹脂組成物⑴中’驗可溶性樹脂⑷為具 〇又鍵且具有驗可溶性基之驗可溶性樹脂(A-2)。 100110287 27 201140239 藉此,由曝光後之間隔件的彈性係數、顯影時可防止間隔件 與石夕基板界面所發生之底割(undercut,剝離)的觀點而言屬 較佳。 本發明之感光性樹脂組成物(1)可含有光聚合性化合物 (G)。藉此,於曝光後之曝光部中,交聯密度變高。藉此, 由於彈性係數提升,故可提升形狀保持性。又,光聚合性化 合物(G)可為單獨1種或2種以上之組合。 本發明之感光性樹脂組成物(1)係在僅含有具光聚合性雙 鍵且具有驗可雜基讀可雜錢(A_2)作秘可溶性樹 脂(A)時,本發明之感光性樹餘成物⑴可含有光聚合性化 亦可不含。此時,不論本發明之感光性樹:組成 物⑴中是否含有光聚合性化合物(G),均需考慮到曝光後之 圖案的彈性係數、顯料在_射基板界面發生 藉此而予以適當選擇。 :在感光性樹脂組成物⑴僅含有不具光聚合 -有驗可祕敲料雜樹脂(Α·⑽ ⑷的情況,本發明之感光性樹脂组成物⑴係==脂 化合物(G)。 有光4合性 光聚合性化合物(G)係藉由照射光而進行 並為具有光聚合性雙鍵的化合物。作為光=的化合物 ⑹’可舉例如具有絲合性雙鍵之光聚合^性化合物 性募聚物、於主鏈或側鏈具有光聚合 I體、光聚合 100110287 ......... 罐的樹月旨等。 28 201140239 作為光來合性單體,可舉例如雙紛A乙二醇改質二(曱基) 丙稀@夂酉曰、異二聚氰酸乙二醇改質二(曱基)丙婦咖旨、三丙 一醇一(曱基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯單硬脂 酉文酉曰、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(曱基)丙烯 酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(曱基) 丙烯g文S曰、二羥曱基丙烧丙二醇三(甲基)丙烯酸酯、三羥甲 基丙烷乙二醇三(曱基)丙烯酸酯、異三聚氰酸乙二醇改質三 (曱基)丙烯酸酯、二季戊四醇五(曱基)丙烯酸酯、二季戊四 醇六(曱基)丙烯酸酯、季戊四醇四(曱基)丙烯酸酯等。 作為光聚合性寡聚物,可舉例如胺基甲酸乙酯(曱基)丙烯 酸酯、環氧基(曱基)丙烯酸酯等。 作為於主鏈或側鏈上具有光聚合性雙鍵之樹脂,可舉例如 對具有(曱基)丙烯酸構造單位之(甲基)丙烯酸系樹脂的羧基 使環氧丙基(甲基)丙烯酸酯之環氧丙基反應的樹脂;對具有 環氧丙基(曱基)丙烯酸酯構造單位之(曱基)丙烯酸系樹脂之 環氧丙基使(曱基)丙烯酸之羧基反應的樹脂。於主鏈或側鏈 上具有光聚合性雙鍵的樹脂的分子量,較佳為5〇以上且 5000以下。 另外,作為光聚合性化合物(G),可舉例如具有親水性基 或親水性構造的光聚合性化合物(G-1)。本發明之感光性樹 脂組成物藉由含有具親水性基或親水性構造的光聚合性化 合物(G-υ’可減低圖案化處_之_。作為親水性基或 100110287 29 201140239 親水性構造,可舉例如醇性羥基等之親水性基、氧基乙烯構 造、氧基兩烯構造等之親水性構造。 如此,本發明之感光性樹脂組成物(1)含有具親水性基或 親水性構造之光聚合性化合物(G_1}❶藉由賦予親水性基或 親水性構造,败其與水的親和性提升。藉此,感光性樹脂 組成物容㈣解於驗顯影液中。因此可減傾案化後之殘 渣。 作為具親水性基或親水性構造之光聚合性化合物㈣), 可舉例如具_基之__化合物(g i i)、具有氧基乙 烯構造或氧基丙稀構造之丙烯酸系化合物((Μ_2)等。此等 之中較佳為具有羥基之丙烯酸系化合物(G l i)。如上述, 本發明之感光性樹脂組成物因為含有丙烯酸系化合物 (G-1-1)或丙稀酸系化合物(0}小2),故圖案化性(顯影性邊 作為具有經基之丙烯酸系化合物(G_M),較佳為對環氧 化合物的縣基使(?基)輯岐應而加成的化合物,且體 可舉例如對乙二醇二環氧丙基峻加成了甲基丙烯酸的:人 物、對乙二醇二環氧丙基醚加成了丙烯酸的化合物、對丙二 醇二環氧丙基醚加成了甲基丙烯酸的化合物、對丙二醇一巧 氧丙基醚加成了丙烯酸的化合物、對三丙二酿_ 衣 一岬一i展氧丙基醚 加成了 f基丙稀酸的化合物、對三丙二酿_ s & 一畔一衣軋丙基醚加成 了丙烯酸的化合物、對雙酚A二環氧丙基醚加成了甲美丙 100110287 30 201140239 烯酸的化合物、對雙酚A二環氡丙基醚加成了丙烯酸的化 合物等。 作為對具有羥基之丙烯酸系化合物(Gqq)中的環氧化合 物、亦即(曱基)丙烯酸所加成之環氧化合物,由形狀保持性 亦優越的觀點而言,較佳為具有芳香環之環氧化合物。具有 羥基之丙烯酸系化合物(G-Μ)中,選自下式(11)之中的丄種 以上化合物除了殘潰之減低效果以外,由形狀保持性亦優越 的觀點而言屬較佳。 [化1] ^ CHj 心 〇
(11-2) (11-3) °" ° Η 六。-1 斗。 (114) 0 (11) 本發明之感光性樹脂組成物(1)中之具有親水性基或親水 性構造之光聚合性化合物(G_ 1)的含量並無特別限定’較佳 為1重量%以上且20重量%以下。特佳為2重量%以上且8 100110287 31 201140239 重量%以下。若具有親水性基或親水性構造之光聚合性化合 物(G-1)的含量為上述範圍内,職殘渣之減低效果與形狀 保持性之雙方性能提高的效果特別優越。 另外,作為光聚合性化合物(G),可舉例如多官能光聚合 性化合物(G-2)。藉由使本發明之感紐樹脂㈣物含有多 官能光聚合性化合物(G_2),可與上述驗可溶性樹脂(A)一起 更加提升圖案化性。多官能光聚合性化合物(G 2)係與具有2 個以上光聚合性雙鍵且具有親水性基或親水性構造光聚合 性化合物(G-1)相異的光聚合性化合物。於此,與具有親水 性基或親水性構造之光聚合性化合物(Gd)相異,係指構 造、分子量等相異。 作為多官能光聚合性化合物(G_2),可舉例如甘油二曱基 丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三曱基 丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三丙烯酸酯、二 季戊四醇六丙烯酸酯等。 作為多官能光聚合性化合物(G-2),較佳為3官能以上之 多官能光聚合性化合物(G-2)。本發明之感光性樹脂組成物 因含有3官能以上之多g能光聚合性化合物(ο ]),即使在 實質上不含填充材的情況下形狀保持性仍優越。 作為3官能以上之該多官能光聚合性化合物(G_2),可舉 例如二經曱基丙院二甲基丙烯酸酯、季戊四醇三丙稀酸醋 等。藉此’三維性地發生光交聯’光交聯密度變高,熱時彈 100110287 32 201140239 性係數不變低。因此,在實f上不含填充材的情況下形狀保 持性仍優越。 本發明之感光性樹脂組成物(丨)中之多官能光聚合性化合 . 物(G·2)的含量並無特別限定,較佳為5重量%以上且50重 量%以下。特佳為10重量%以上且4〇重量%以下。若多官 能光聚合性化合物(G-2)含量越過上述上限值,則有密黏強 度變低的情形。另-方面,若未滿上述下限值,則有形狀保 持性變低的情形。 具有親水性基或親水性構造之光聚合性化合物(G l)、與 多官能光聚合性化合物(G-2)(尤其是3官能以上之該多官能 光聚合性化合物(G-2))可予以併用。藉此,可得到形成圖案 時之殘渣減低效果及圖案之形狀保持性效果之雙方優越的 感光性樹脂組成物。於併用的情況,具有親水性基或親水性 構造之光聚合性化合物(G-1)之含量相對於多官能光聚合性 化合物(G-2)之含量的比(具有親水性基或親水性構造之光 聚合性化合物(G-1)之含量/多宫能光聚合性化合物(G_2)之 含里)並無特別限疋’較佳為0.05以上且1.5以下β特佳為 - 〇. 1以上且以下。若具有親水性基或親水性構造之光聚 - 合性化合物(G_1)相對於多官能光聚合性化合物(G-2)的比為 上述範圍内’則除了上述殘渣減低效果及形狀保持性效果以 外’作業性、細微加工性、可靠性亦優越。 本發明之感光性樹脂組成物(1)係含有驗可溶性樹脂 100110287 33 201140239 ㈧,驗可雜_㈧含有歧叙魏 成物含有絲合性化合物⑹1。1 因此,藉由對本發明之感光 性職組成物⑴進行曝光及鹼顯影,可形 光性樹脂組成物層。又,其後^ α 再後错由加熱硬化,可形成經圖案 化之保護膜,例如抗鋅層。 本發明之感紐樹肋成物⑴係含有光聚合起始劑⑻。 光聚合起始劑⑻係藉由吸收曝私並分解而產生自由其, 發揮使具有光反應性雙鍵之驗可溶性樹脂(Α)或光聚合化 ^物⑼聚合的機能。然後’本發明之感紐樹脂組成物⑴ 錯由含有光聚合料劑⑻,而料及顯影後之圖案化性變 高。 作為光聚合起始劑(B)並無特別限定,可舉例如二苯基 ’、苯乙_、苯偶姻、苯偶姻異丁基喊、苯偶姻苯甲酸甲醋、 苯偶姻笨曱酸、苯偶姻甲細1基苯基硫化物、节基、节 基二曱基縮酮、二苄基、二乙醯基等。此等之中,較佳為圖 案化性優越之二苯基酮、苄基二曱基縮酮。 本發明之感光性樹脂組成物(1)中,光聚合起始劑(B)之含 置並無特別限定,較佳為感光性樹脂組成物整體之0.5重量 %以上且1〇重量%以下,特佳i重量%以上且5重量%以下。 右光聚合起始劑(B)之含量未滿上述範圍,則有使光聚合起 始之效果變低的情形。又,若超過上述範圍,則反應性過高, 有使用前之感光性樹脂組成物的保存性或圖案化後之解析 100110287 34 201140239 性變㈣料。因此’藉由使光聚合起始軸 上述範圍,則可提供使光聚合起始之效果、*提里= 組成物 本發明之 :及圖案化後之解析性之間的均衡優越J光二 感光性樹脂組成物⑴係含有最大吸 ^細以上且25⑽nm以下之範圍内岐外線吸收劑⑼。 外線之遮光性 發明之感光性樹脂組成物⑴因含有紅外線吸收雜),而 使感光性樹脂組成物硬化所得之⑽層等之保護膜具有紅 紅外線吸收劑(D)具有吸收紅外線之性f。紅外線吸收劑 (D)之最大吸收波長為8〇〇腹以上且25〇〇帅以下之範圍 内。而且,紅外線吸收劑⑼之最大吸收波長的穿透率為15% 以下、較佳1%以上且10%以下,特佳2%以上且5%以下。 另外,紅外線吸收劑(D)之熱分解溫度較佳為2〇〇t以上、 特佳2贼以上。麻’在將受光裝置之絲板與電路基板 進行銲接的步财,紅外線料_)不致變f。藉此,即 使在銲接後仍可保有吸收上述紅外線的性質。 作為紅外線吸收劑(D),可舉例如金屬硼化物、氧化鈦、 氧化锆、錫摻雜氧化銦(ITO)、銻摻雜氧化錫(AT〇)、偶氮化 合物、胺鏘(aminium)化合物、亞胺鑌(iminium)化合物、蒽 醌化合物、花青化合物、二銨(diim〇nium)化合物、方酸 (squarylmm)化合物、酞菁化合物、萘菁化合物、蒽醌 100110287 35 201140239 (anthraquinone)化合物、萘酿i化合物、二硫醇化合物、聚甲 炔(polymethine)化合物。 (GdB6) (HoB6) (EuB6) (YbB6) 六硼化鈥 六硼化銪 六硼化镱 六棚化#5 作為金屬硼化合物,可舉例如六硼化鑭(LaB6)、六硼化镨 (PrB6)、六硼化鈦(NdB6)、六硼化鈽(CeB6)、六硼化釓 六硼化铽(TbB6)、六硼化鏑(DyB6) 六硼化釔(ΥΒό)、六硼化釤(SmB6) 六硼化铒(ErB6)、六硼化铥(TmB6) 六硼化镏(LuB6)、六硼化锶(srB6) (CaB0)、棚化鈦、硼化鍅(ZrB2)、硼化铪(HfBj、硼化 釩(VB2)、硼化鈕(TaB2)、硼化鉻(CrB及CrB2)、硼化鉬 (MoB2、M〇2B5及MoB)及硼化鎢呢叫及此等之混合物等。 偶氮化合物係具有·N=N•鍵結之化合物,且最大吸收波長 為800nm以上且25⑽nm以下之範圍内的化合物。更具體而 =系:有购·鍵結’且於姆鍵結之對位上具有經基 或由綠衍生之官能基的化合物。作為偶氮化合物,可舉例 如下述一般式(i)所示之偶氮化合物: r!-n=n-r2 ⑴ 式(:)中’…2為芳香族基,於偶氣基之對位 100110287 36 201140239 [化2]
胺鑕化合物係胺之非共有電子對電子之一個被氧化而成 為陽離子,與陰離子形成鹽的化合物,且最大吸收波長為 800nm以上且2500nm以下之範圍内的化合物。作為胺繙化 合物,可舉例如下述一般式(2): 100110287 37 201140239 Η匕3]
所示之胺鑕化合物。上述一般式(2)中,R3為碳數1〜6之烷 基,A為芳香族基,X為選自由Γ、BF4、C104_、AsF6_、 SbFV所組成群之一種。又,R3為相同或相異。 亞胺鏽化合物(銨化合物)係具有亞銨鑌鍵、亦即下述鍵: [化4]
,且最大吸收波長為800nm以上且2500nm以下之範圍内的 化合物。作為亞胺鏽化合物,可舉例如具有1個亞胺鑌鍵的 亞胺鑌化合物、具有2個亞胺鑌鍵之二銨化合物(二亞胺鏽 化合物)。又,亞胺鏽化合物可舉例下述一般式(3): [化5]
所示之亞胺鏽化合物。又,二銨化合物可舉例如下述一般式 100110287 38 201140239 (4): [化6]
⑷ 所示之二銨化合物。上述一般式(3)中,R4為選自由氫原子、 碳數1~6之烧基、烧氧基、烧基烧氧基所組成群之一種, R5為含有芳香族基之基,X為選自由r、BF4_、C104_、AsF6_、 SbF6·所組成群之一種。又,上述一般式(4)中,R6為選自由 氫原子、碳數1〜6之烷基、烷氧基、烷基烷氧基、具有芳香 族基所組成群的一種,X為選自由Γ、BF4·、C104_、AsF6·、 SbF6·所組成群之一種。 更具體而言,作為亞胺鑌化合物,可舉例如下式(5-1)及 (5-2): [化7] h3c 3 (5-1)
>-〇-n=〇^n" 9H4C c4h9 C4Hq (5-2) 所示之亞胺鑌化合物。又,作為二銨化合物,可舉例如下式 100110287 39 201140239 (6-1)及(6-2): [化8]
3 p4^9 (6-1) 3 3
HC
(6 — 2) 3 c4h9 所示之二銨化合物。 酞菁化合物係具有下述一般式(7): [化9]
所示之構造,且最大吸收波長為800nm以上且2500nm以下 之範圍内的化合物。上述一般式(7)中,Me表示鋁、鈦、鐵、 100110287 40 201140239 銘、錫、銅、鋅、猛、錫、石夕、鎵、把、鎮等之金屬元素。 又,上述一般式(7)所示之酞菁化合物亦可於芳香族環上具 有取代基。 萘菁化合物係具有下述一般式(8): [化 10]
所示之構造,且最大吸收波長為800nm以上且2500nm以下 之範圍内的化合物。上述一般式(8)中,Me表示鋁、鈦、 鐵、钻、錫、銅、鋅、锰、錫、石夕、鎵、妃、鎮等之金屬元 素。又,上述一般式(8)所示之萘菁化合物亦可於芳香族環 上具有取代基。 蒽醌化合物係具有下式: [化 11] 100110287 41 201140239
所示之蒽醒構造,且最大吸收波長為800nm以上且2500nm 以下之範圍内的化合物。例如,作為蒽酿> 化合物,可舉例如 下式(9): [化 12] (R1、2、 〇
(R13X (9) 所示之蒽醌化合物。上式(9)中,R12及R13為具有氮原子之 取代基、羥基、具有芳香環之取代基,P及q為1〜3之整數。 又,R12及R13可為相同或相異。更具體而言,作為蒽醌化 合物,可舉例如下式(9-1): [化 13] 100110287 42 201140239
〇 OH
(9-1) 所示之蒽醌化合物,下式(9-2): [化 14]
(9-2) 所示之蒽醌化合物,下式(9-3): [化 15] ΝΗ Ο ΝΗ
所示之蒽醌化合物。 二硫醇•金屬錯合物化合物係具有下式(10): [化 16] 100110287 43 201140239
〆\s (R3) Vs
(10) 所示之構造’且最大吸收波長為800nm以上且25〇〇nm以下 之範圍内的化合物。上式(1〇)中,R3表示碳數丨〜4之烷基、 务基、^烧基、烧胺基、鹵素之任一種’ Μ表示鎳、|白、 Ιε之任一種。 此等紅外線吸收劑(D)中,較佳係紅外線吸收能力佳、且 耐熱性優越的金屬硼化合物。 紅外線吸收劑可為單獨1種或2種以上之組合。而且, 本發明之感光性樹脂組成物(1)中,藉由組合最大吸收波長 相異之複數的紅外線吸收劑,則可得到可遮阻廣範圍波 長之紅外線的抗銲層等之保護膜。例如,藉由組合最大吸收 波長為871nm之紅外線吸收劑、最大吸收波長為9i3nm之 紅外線吸收劑、與最大吸收波長為966nm之紅外線吸收劑, 則可遮阻875nm以上且960nm以下之區域的紅外線。 尚且,本發明中,所謂紅外線吸收劑(D)之最大吸收波長, 係指在藉分光光線穿透率分析時,穿透率最小的波長。 另外,紅外線吸收劑(D)之熱分解溫度係藉熱重量變化分 析所測定之值。 本發明之感光性樹脂組成物(1)中,各紅外線吸收劑(D)的 100110287 44 201140239 含里並無特別限^ ’較佳為感光性樹脂組成物整體之0.01 重篁%以上且15重量%以下。特佳為〇]重量%以上且1〇 重量%以下。藉由使紅外線吸收劑(D)之含量為上述下限值 以上’則抗#干層等之保護膜遮阻紅外線的效果變高。又,藉 由使紅外線吸收劑(D)之含量為上述上限值以下,則可使波 長400nm以上且70〇nm以下之可見光穿透率為$ 〇%以上。 又,於使用1種紅外線吸收劑(D)作為紅外線吸收劑(D)時, 各紅外線吸收劑(D)的含量係指其【種紅外線吸收劑(D)之含 量。又,在使用最大吸收波長相異之複數之紅外線吸收劑的 情況’各紅外線吸收劑(D)的含量係指所使用之複數之紅外 線吸收劑的各別含量。例如,在組合使用最大吸收波長為 871nm之紅外線吸收劑、最大吸收波長為913nm之紅外線 吸收劑與最大吸收波長為966nm之紅外線吸收劑的情況, 各紅外線吸收劑的含量較佳為感光性樹脂組成物整體的 〇.〇1重量%以上且15重量%以下。特佳為〇」重量%以上且 10重量%以下。 另外,於使用最大吸收波長相異之複數之紅外線吸收劑的 情況’所使用之紅外線吸收劑(D)的合計含量較佳為感光性 樹脂組成物整體之〇·〇1重量%以上且15重量❶/。以下。特佳 為0.1重量%以上且10重量%以下。 另外’本發明之感光性樹脂組成物(1)中之紅外線吸收劑 (D)的平均粒徑並無特別限定,較佳為ΙΟμπι以下。更佳為 100110287 45 201140239 5μπι以下。又,此處所謂「平均粒徑」係指藉雷射繞射散射 法所求得之粒度分佈中累積值5〇%的粒徑(D5〇)。 在紅外線吸收_)之平均粒徑為上述上限值以上時,於 形成抗録㈣,因厚度方向積體變大岐粒子間發生空隙, 紅外線的穿透率變高。因此,若增加紅外線吸㈣之添 加量,則無法降低紅外線之穿透率。 另-方面,藉由使紅外線吸收劑⑼之平均粒徑為上述上 限值以下,_紐樹舰成物⑴中之紅外線吸收劑⑼的 t散性變佳,可減低厚度方向的體積。亦即,於形成抗銲層 由於朝平面方向祕的粒切加,故叫銲層整體而 & ’可提高紅外線吸收劑⑼粒子所佔有的填充率。社果, 可使抗銲層整體之紅外線穿透率降低。 低广:二使紅外線吸收劑(D)的含有量較少,仍可確實降 低紅外線區域的穿透率、 j峰貫降 性。 可依低成本得到紅外線遮阻 機物:可平均粒徑之紅外線吸收劑⑼中,屬於無 之形成方二與件進仃破碎而形成。作為紅外線吸收劑(D) 其次,針如球磨法或珠磨法等。 發明之感光如^之感紐樹脂組成物(2)進行說明。本 本發明之 ^組祕(2)為与之性樹脂組成物。 使曝光部分藉鹼顯影液之顯影 部分對顯影硬之係藉由照射曝光光,而曝光 ^00110287 46 201140239 被去除。又’在藉曝光光之照射及驗顯影進行了圖案化後, 曰…、進行…、硬化而成為熱硬化物。本發明之感光性樹脂組 成物(2)係含有驗可溶性樹脂⑷、光酸產生劑(〇與最大吸收 波長為8OOnm以上且25〇〇nm以下之範圍内的红外線吸收劑 (D); 藉由知射曝光光’使曝光部分之光酸產生劑(C)分解。藉 此產生酸。因此’曝光部分對驗顯影液之溶解性增加。曝光 光為备、外、線幸交佳為36〇nm以上且伽咖以下之紫外線。 作為曝光光之光源並無特別限制,可使用g線、i線、激分 子雷射等之光源。 本發明之感光性樹脂組成物⑺中之驗可溶性樹脂㈧,為 對驗顯影液呈可溶性的樹脂,於分子内具有驗可溶性基。 又,驗可溶性樹脂(A)係為使彡後之化的感光性樹 脂組成物層被熱硬化’而㈣性錄、醇性羥基,基、酸 針基、胺基、氰_基等之藉加熱而進行熱硬化反應的熱反 應基。 本發明之感光性樹脂組成物⑺中,感光性樹脂組成物所 含有之驗可雜職⑷係麵絲照雜胁顯影液進行 顯影時,曝光部分溶解於驗顯影液中而被去除。藉此,可藉 曝光光照射選擇性地進行圖案化。因此,本發明之感光輯 脂組成物(2)中之驗可溶性樹脂⑷,储由因曝光光坪射以 使光酸產生劑分解而產生酸的作用,可進行驗顯影的樹脂。 100110287 201140239 本發明之感光性樹脂組成物(2)係藉曝光光之照射及鹼顯 影而經圖案化後,進行加熱而予以熱硬化,藉此成為半導體 裝置之抗銲層等之保護膜。然後,本發明之感光性樹脂組成 物(2)視藉由加熱而進行熱硬化時之作用,而鹼可溶性樹脂 (A)有以下2種樹脂: (0藉由與環氧樹脂等之熱硬化性樹脂進行反應而形成硬 化物的熱硬化性樹脂加成型之樹脂 (ii)藉由鍵結於本身之分子鏈上的官能基於分子鏈内進行 環化反應而形成硬化物的自己縮合型之樹脂 尚且,在(i)熱硬化性樹脂加成型之樹脂的情況,本發明之 感光性樹脂組成物(2)係含有與⑴熱硬化性樹脂加成型之樹 脂進行熱硬化反應的熱硬化性樹脂。又,在⑴)自己縮合型 之樹脂的情況,本發明之感光性樹脂組成物(2)可含有熱硬 化性樹脂,亦可不含。 本發明之感光性樹脂組成物(2)之鹼可溶性樹脂(A)中,作 為(i)熱硬化性樹脂加成型之樹脂,可舉例㈣祕清漆樹 月曰&酿胺I等,更具體可舉例如甲紛型、紛型、雙酴a 型、雙紛F型、鄰苯二驗型、間苯二龄型、五倍子紛型等之 祕清漆樹脂’料妓樹脂、織苯乙_脂、甲基丙稀 酸樹脂、丙烯酸系樹脂、含餘基、絲等之環狀烯烴系樹 月曰。又’本發明之感光性樹脂組成物⑺中之驗可溶性樹脂 (A) ’包括曱齡、雙盼A、雙酚F、鄰苯二酚、間苯二紛、 100110287 48 201140239 五倍子紛等之重複單位之數為⑽的低分子量化合物,亦包 括甲酚型酚型、雙酚八型、雙鹼F型、鄰苯二酚型、間 苯一盼型、五倍子盼型等之㈣清漆樹脂等之重複單位之數 為2個以上的咼分子量化合物。 另外’本發明之感光性樹脂組成物(2)中之驗可溶性樹脂 (A)中’作為(11)自己縮合型之樹脂,有如聚醯胺系樹脂,更 具體可舉例如m笨并μ構減聚醯亞胺構造之至少 一者,且於主鏈或側鏈上具有羥基、羧基、醚基或酯基的樹 月曰,具有聚苯并呤唑前驅物構造之樹脂,具有聚醯亞胺前驅 物構造之樹脂,具有聚醯胺酸酯構造之樹脂等。 另外,本發明之感光性樹脂組成物(2)亦可含有含羧基之 丙烯酸樹脂般之鹼可溶性熱可塑性樹脂。 本發明之感光性樹脂組成物(2)中之鹼可溶性樹脂(Α)的 s量並無特別限定,在下述情況下較佳為下述範圍内。例 如,在本發明之感光性樹脂組成物(2)不含後述之無機填充 材的情況,本發明之感光性樹脂組成物(2)中之鹼可溶性樹 脂(Α-1)的含量為1〇重量%以上且重量%以下,較佳15 重量%以上且70重量%以下。又,在本發明之感光性樹脂 組成物(2)含有後述之無機填充材的情況,本發明之感光性 树脂組成物(2)中之驗可溶性樹脂(Α)的含量係相對於由本 發明之感光性樹脂組成物(2)減去該無機填充劑之成分的合 汁,較佳為15重量%以上且6〇重量以下、特佳20重量% 100110287 49 201140239 以上且50重重%以下。若鹼可溶性樹脂(A)之含量未滿上述 下限值,則有於曝光、顯影時發生感光性樹脂組成物之殘渣 的情形。另〆方面’若超過上述上限值,則有於曝光、顯影 時形成圖索之感光丨生柯月曰、纟且成物的膜減少變大,而發生圖案 厚度偏差的情況。 本發明之光性樹脂組成物(2)係含有光酸產生劑(〇。光 酸產生劑(C)係吸收曝光光而進行分解以產生酸,發揮使感 光性樹脂組成物之曝光部對鹼顯影液之溶解性提升的機 能。而且,本發明之感光性樹脂組成物(2)係藉由含有光酸 產生劑(C) ’而可進行曝光及顯影後之圖案化。 作為光酸產生劑(C) ’可舉例如酚化合物與丨,2_萘醌_2_二 疊氮-5-項酸或u•察醌_2_二曼氮斗石黃酸的醋。具體可舉例 如式(16)〜式(19)所*之賴化合物。減產生劑⑹可為一種 或2種以上之組合。 [化Π] 100110287 201140239 Η
Ol <>13
CH3 ch3 Q-NH-(CH2)3—Si—o—Si—(CH2)3-NH-Q ch3 [化 18] 100110287 51 201140239
OQ (17) [化 19] 100110287 52 201140239
100110287 53 201140239 [化 20]
式(16)〜式(19)中,Q為選自氫原子、式(20)及式(21)所示 構造中之任一者。於此,各化合物之Q中,至少一個為式(20) 或式(21)所示構造。 [化 21] 100110287 54 201140239
S〇2 N2 S〇2 (20) (21) 本發明之感光性樹脂組成物(2)中之光酸產生劑(c)的含 量,係相對於鹼可溶性樹脂(A-l)lOO重量份,較佳為}重量 份以上且50重量份以下’特佳10重量份以上且4〇重量份 以下°藉由使光酸產生劑(C)含量為上述範圍内,則感度特 別優越。 本發明之感光性樹脂組成物(2)係含有驗可溶性樹脂 (A),且含有光酸產生劑(C)。如此,藉由對本發明之感光性 樹脂組成物(2)進行曝光及鹼顯影,則可形成經圖案化之感 光性樹脂組成物層。又,其後,藉由使其加熱硬化,可形成 經圖案化之半導體裝置之抗銲層等半導體裝置之保護膜。 本發明之感光性樹脂組成物(2)係含有最大吸收波長為 800nm以上且25〇〇mn以下之範圍内的紅外線吸收劑①)。 本發明之感光性樹脂組成物(2)因含有紅外線吸收劑(D),而 使感光性樹脂組成物熱硬化所得之抗銲層等之保護膜具有 紅外線之遮光性。 100110287 55 201140239 本發明之感光性樹脂組成物(2)中之紅外線吸收劑(D) ’係 與本發明之感光性樹脂組成物(1)中之紅外線吸收劑(D)相 同。 本發明之感光性樹脂組成物(2)中之紅外線吸收劑(D)可 為單獨1種或2種以上之組合。而且,本發明之感光性樹脂 組成物(2)中’藉由組合最大吸收波長相異之複數的紅外線 吸收劑(D) ’則可得到可遮阻廣範圍波長之紅外線的抗銲 層。例如,藉由組合最大吸收波長為871nm之紅外線吸收 劑、最大吸收波長為913nm之紅外線吸收劑、與最大吸收 波長為966nm之紅外線吸收劑,則可遮阻875nrn以上且 960nm以下之區域的紅外線。 本發明之感光性樹脂組成物(2)中’各紅外線吸收劑(]〇)的 含里並無特別限定’較佳為感光性樹脂組成物整體之〇〇1 重量。7°以上且15重量%以下。特佳為G.1重量%以上且1〇 重量%以下。藉由使紅外線吸收劑(D)之含量為上述範圍 内則抗銲層專之保護膜遮阻紅外線的效果變高。又,於使 用1種紅外線吸收劑(D)作為紅外線吸收劑⑼時,各紅外線 吸收劑(D)的含量係指其丨種紅外線吸收劑①)之含量。又, 在使用最大吸收波長相異之複數之紅外線吸收_情況,各 紅外線吸收劑⑼的含量係指所使用之複數之紅外線吸收劑 的各別含量,如,在組合使用最大吸收波長為奶誰、 9Unm及%6細之三種紅外線吸收劑的料,各紅外線吸 100110287 56 201140239 诏勺S里車乂佳為感光性樹脂組成物整體的0.01重量%以 上且15 4置0/°以下’特佳為0.1重量%以上且10重量。/。以 下 本么月之感光性樹脂組成物(2),紅外線吸收劑(D)的平均 r 特⑺限疋’可設為與本發明之感光性樹脂纟且成物⑴ 相同的尺寸。 卜在使用最大吸收波長相異之複數之紅外線吸收劑 時’所使用之紅外線吸收_)之合計含量較佳為感光性樹 脂組成物整體之請重量%以上且15重量%以下,特佳〇」 重量%以上且10重量°/〇以下。 成以雜驗成物⑴及本發明之感光性樹脂組 成物(2)可S有聽性減與縣德合物(E)。#此 :=一。又,可提高與構成感光性樹脂組成 ::二的相溶性。因此,可減低曝光及顯影後之紗 徒间了 1分子中之羧基濃度者,其對鹼 - ::::冓_過高’則化合物⑻分子間之結二t =冋J成感光性樹餘成物之其他成分_相溶性㈣ 低。因此’感光性樹脂組成财除了幾基以外 文 對驗顯影液之親和性不如絲般之雜瘦 3具有 物⑻)。藉此,可兼顧到祕顯影液之親和㈣及^物(化合 光性樹腊組成物之其他樹脂成分間的相溶性。”構成感 具有朌性經基與縣之化合物⑹的重量平均分子旦、 100110287 57 201140239 特別限定,較佳為1〇〇以上且娜以下,更佳為i5〇以上 且邏以下,特佳200以上且2_以下。藉由使化合物⑻ 之重量料分子㈣上述顯’麻動轉㈣影液之親和 性以及與構成感光性樹脂組成物之其他_成分間之相溶 性的效果提升。於此,重量平均分子量係依與上述相同之方 法所測定。 ”有紛基與鼓基之化合物(E)若為具有射纟經基與叛 基者’則無特別限定,可舉例如下述-般式(22)〜(24)所示之 化合物。本發明之感紐樹脂組成物储由含有下述一般式 Γ〜(2ΓΓ之化合物料具㈣_基與縣之化合物 )/低曝光及顯影後之_的效果更加提高。 [化 22]
(22) (23)
100110287 58 201140239 上述一般式(22)中,R21表示芳香族以外之有機基,a及b 為1〜3之整數。a及b並無特別限定,較佳係a= 1且b=2。 ' 藉由設為a=l且b=2,則可兼顧能減低感光性樹脂組成物之 ' 曝光及顯影後之殘渣的效果以及提升與構成感光性樹脂組 成物之其他樹脂成分間之相溶性的效果。 R21若為芳香族以外之有機基,則無特別限定,可舉例如 單鍵、碳數1〜20之直鏈或分枝狀之烴基。在b為1的情況, 具體例可舉例如亞曱基、伸乙基、正伸丙基、異伸丙基、異 伸戊基、第二伸戊基、第三伸戊基、甲基丁基、1,1-二曱基 伸丙基、正伸己基、1-曱基伸戊基、2-曱基伸戊基、3-曱基 伸戊基、4-曱基伸戊基、1-乙基伸丁基、2-乙基伸丁基、3-乙基伸丁基、1,1_二曱基伸丁基、2,2-二甲基伸丁基、3,3-二曱基伸丁基、1-乙基-1-甲基伸丙基、正伸庚基、1-甲基伸 己基、2-曱基伸己基、3-曱基伸己基、4-甲基伸己基、5-曱 基伸己基、1-乙基伸戊基、2-乙基伸戊基、3-乙基伸戊基、 4-乙基伸戊基、1,1-二甲基伸戊基、2,2-二曱基伸戊基、3,3-二曱基伸戊基、4,4-二曱基伸戊基、1-丙基伸丁基、正伸辛 . 基、1-曱基伸庚基、2-曱基伸庚基、3-曱基伸庚基、4-甲基 . 伸庚基、5-曱基伸庚基、6-曱基伸庚基、1-乙基伸己基、2-乙基伸己基、3-乙基伸己基、4-乙基伸己基、5-乙基伸己基、 6-乙基伸己基、1,1-二甲基伸己基、2,2-二曱基伸己基、3,3-二曱基伸己基、4,4-二曱基伸己基、5,5-二甲基伸己基、1- 100110287 59 201140239 丙基伸戊基、2-丙基伸戍基等;較佳為碳數1〜6之直鏈或分 枝狀之基。藉由將碳數設為卜6,則可使能減低感光性樹脂 組成物之曝光及顯影後之殘渣的效果以及與構成感光性樹 脂組成物之其他樹脂成分間之相溶性之效果提升。 另外’ b為2的情況,具體可例示下述一般式(25)所示之 基。 [化 25] 氺 R23一c一R24 (25) 氺 上述一般式(25)中,R23及R24表示氫原子、碳數1〜20之 直鏈或分枝狀之烷基、碳數1〜2〇之直鏈狀伸烷基(未端為羧 基)、羧基。*上鍵結著具有一般式(22)中之酚性羥基的笨 環。其中,R23或R24雙方不同時為氫原子、碳數丨〜扣之直 鏈狀或分枝狀之烷基,R23或R24之一者為氫原子、碳數K2〇 之直鏈狀或分枝狀烷基的情況,其一者為碳數卜扣之直鏈 狀伸烷基(末端為羧基)。 上述一般式(25)中之m β之至少一者’為碳數⑽ 之直鏈或分枝狀之伸烷基(末端為羧基)。藉此,可減低感光 性樹脂組成物之曝光及顯影後之殘邊。又,可提高使與構、 感光性树爿θ組成物之其他樹腊成分間之相溶性提弁 100110287 60 201140239 果。進而,特佳為碳數之直鍵或分枝狀之伸烧基(末端 為叛基)。 • 在b為3的情況,具體·^例示下述一般式(26)所不之基。 ' [化 26] R25 *—C— * (26)
I 木 上述一般式(26)中,R25表示碳數1〜20之直鏈或分枝狀之 伸烷基(末端為羧基)、羧基,氺上鍵結著具有上述一般式(22) 中之酚性羥基的苯環。 上述一般式(26)中’ R25為例如碳數1〜1〇之直鏈或分枝狀 之伸烷基(末端為羧基)。藉此,可減低感光性樹脂組成物之 曝光及顯影後之殘渣。又,可提高使與構成感光性樹脂組成 物之其他樹脂成分間之相溶性提升之效果。再者,特佳為碳 數1〜6之直鏈或分枝狀之伸烷基(末端為羧基)。 上述一般式(23)中,c及d為卜5之整數。作為上述一般 式(23)所示之化合物,並無特別限定,可舉例如2_經基苯甲 酸、3-經基苯曱酸、4·經基笨曱酸、2>二經基笨曱酸、2,4-二經基苯甲酸、2,5-二經基笨甲酸、2,6.二經基苯甲酸、3,4-二經基苯甲酸、3,4,5_三祕苯甲酸、2,4,6三祕苯甲酸 100110287 61 201140239 等。由減低感光性樹脂組成物之曝光及顯影後之魅的效果 以及與構成感紐樹驗之其他難成㈣之相溶性 之效^高的觀點而言’較佳為2,3·二經基苯甲酸、2,4_二 U甲^、2,5_二經基苯甲酸、2,6·二經基苯甲酸、3,冬 1、苯甲酉夂、3,4,5-三羥基苯甲酸、2,4,6-三羥基苯甲酸。 述奴式(24)令’ e及f為1〜3之整數。e及f並無特別 限=例如ey且f=:2。藉此,可減低感光性樹脂組成物之 曝光及顯影後之殘潰。又,可提高與構錢紐樹脂組成物 之其他樹脂成分間之相溶性之效果。 上述-般式(24)中,R22表示芳香族以外之有機基,並無 特別又可舉例如單鍵、氫原子、碳數1〜20之直鏈狀或 分枝狀之煙基。R22為例如碳數卜⑺之直鏈狀或分枝狀之煙 基藉此,可減低感光性樹脂組成物之曝光及顯影後之殘 渣。又,可提高使與構成感光性樹脂組成物之其他樹脂成分 間之相溶性提权絲。再者,㈣為碳數卜6之直鍵或^ 枝狀之煙基。 作為上述一般式(24)所示之化合物並無特別限定,可舉例 如酚酞、酚酞衍生物等。藉此,酚酞可減低感光性樹脂組成 物之曝光及齡彡後之n並可提升使與構减光性樹脂紅 成物之其他樹脂成分間之相溶性提高之效果。 具有紛性減與絲之化合物(E)之含量並純別限定, 於感光性樹脂組成物中,較佳為0 i重量%以上且30重量% 100110287 62 201140239 以下,更佳0.3重量。/。以上且2〇重量。/Q以下,特佳〇·5重量 %以上且15重量%以下。藉由使化合物(幻之含量為上述範 圍内,則使減低感光性樹脂組成物之曝光及顯影後之殘渣的 效果提高。進而,可確保與構成感光性樹脂組成物之其他樹 脂成分間之相溶性。 本發明之感光性樹脂組成物(丨)及本發明之感光性樹脂組 成物(2)可含有熱硬化性樹脂(F)。藉此,由感光性樹脂組成 物之硬化物所構成之抗銲層與鍍銅層之間的接黏力變高。 料熱硬化性㈣(F)並無制限定,可舉例如祕盤清 漆樹脂、甲紛祕清漆樹脂、雙紛A祕清漆樹脂等之紛 酸清漆_樹脂,可溶轉_料之_脂,雙酴A驾 氧樹脂、㈣F環氧樹脂等之雙_環氧樹脂,祕清_ 氧樹脂、甲祕㈣漆環氧樹脂等之祕清漆型環氧樹脂 ^苯型環氧樹脂、_環氧樹脂、含三4核之環氧樹脂、二 %戊一烯型環氧樹脂、參酚曱烷型環氧樹脂、萘型環氧接 脂、聚錢改質環氧樹脂等之環氧樹脂,脲(尿素)樹脂、: 聚氛胺樹料之具有三錢之樹脂,不飽和聚賴脂、雙摩 •基甲酸崎月旨、二烯丙基酞酸軸 1曰、#咖旨、具有科。«之樹脂、細旨樹脂等。. 德係由可增加感光性樹脂組成物之自由體積、可 ==之透澡率的觀點而言屬較佳。又,可降低感光性 树Μ成物之硬化物的吸水。再者,由可提高透濕率之觀點 100110287 63 201140239 而。特佳為敢祕/月漆型環氧樹脂、甲賴酸清漆型 樹月曰-%戍—烯型每氧樹脂、㈣甲&型環⑽月旨。i 熱硬化性龍附,包括㈣A環氧_、㈣f環氧汽 月曰旨等之雙_環氧樹脂般之重複單位之數為i個的低分子 量化合物’亦包括祕清漆環氧樹脂、甲紛麟清漆環 脂等之雜清漆型環氧樹脂般之重複單位數為2個以切 南分子量化合物。 熱硬化性樹脂(F)之含量並無特別限定,於感光性樹騎 成物中,較佳為1〇重量%以上且7〇重量%以下。更佳為U 重量%以上且65重量%以下。特佳為扣重量%以上且6〇重 量%以下。藉由使熱硬化賴脂(F)之含量為上職圍内,則 可提高抗銲層與鍍銅層間之接黏力。進而,可提高 機械特性。 於使用環氧樹脂作為熱硬化性樹脂(F)時,本發明之感光 性樹脂組成物⑴及本發明之感光性樹脂組成物⑺可含有以 環氧樹脂之硬化劑進行作用的化合物。作為熱硬化性樹脂 十之以環氧_之硬化親行作㈣化合物,並無特別限 定,可舉例如盼衍生物 '紐衍生物、咪唾類等。其中,在 曝光及顯影時酚衍生物具有溶解促進劑之作用。進而> 在f"層之機械特性優越。 作為熱硬化性樹脂(F)中之以環氧樹脂之硬化劑進行作用 的紛竹生物,可舉例如酴紛酸·清漆樹脂、具有伸—其其、 100110287 64 201140239 酚芳烷基樹脂、三苯基曱烷基型酚樹脂、聯苯芳烷基型酚樹 脂、α-萘酚芳烷基型酚樹脂、β_萘酚芳烷基型酚樹脂等。其 中’由減低曝光及顯影後之殘渣的效果變高的觀點而言,較 佳為盼紛酸清漆樹脂。 本發明之感光性樹脂組成物(1)及本發明之感光性樹脂組 成物(2)中,可不損及本發明目的之範圍内可含有紫外線吸 收背丨均平劑、偶合劑、抗氧化劑等之添加劑。 本’X明之感光性樹脂組成物(1)及本發明之感光性樹脂組 成物(2)可含有無機填充材。 在顯影後之殘渣減低的要求較高時,本發明之感光性樹脂 組成物(1)及本發明之感光性樹脂組成物(2)之無機填充材的 3里’較佳為感光性樹脂組成物整體之大於〇重量%且5重 量%以下。 另方面’在耐熱性或尺寸穩定性、耐濕性等之特性要求 較门的凊况,本發明之感光性樹脂組成物(1)及本發明之感 光&_日組成物(2)可進而含有無機填充材。作為此種無機 真充材可舉例如:滑石、燒成黏土、未燒成黏土、雲母、 _ :之石夕酉夂鹽’氧化鈦、氧化銘、溶融二氧化石夕(溶融球 卜^化石夕、溶融破碎二氧化石夕)、結晶二氧化石夕等之二氧 ^粉末等的氧化物’魏♦碳祕、水滑石等之碳酸鹽, ^化^虱氧化鎂、氫氧化鱗之1氧化物,硫酸鎖、硫 瓜駄鈣等之硫酸鹽或亞硫酸鹽,硼酸鋅、偏硼酸鋇、 100110287 65 201140239 硼酸鋁、硼酸鈣、硼酸鈉等之硼酸鹽,氮化鋁、氮化硼、氮 化矽等之氮化物等。此等無機填充材可為單獨丨種或組合2 種以上。此等之中,較佳為熔融二氧化矽、結晶二氧化矽等 之二氧化矽粉末,特佳為球狀熔融二氧化矽。 本發明之感光性樹脂組成物(1)及本發明之感光性樹脂組 成物(2)係藉由含有無機填充劑,而使將感光性樹脂組成物 硬化後之耐熱性、耐濕性、強度等變高。又,無機填充材之 形狀並無特別限定,較佳為真球狀。 無機填充材之平均粒徑並無特別限定,較佳為5nm以上 且50nm以下,特佳為l〇nm以上且3〇nm以下。無機填充 材之平均粒徑若未滿上述範圍,則因無機填充材容易凝集, 故有於感光性樹脂組成物中無機填充材之分佈發生偏差的 情形。又’若超過上述範圍,則有曝光及顯影所得之解析性 變得過低的情形。 作為本發明之感光性樹脂組成物⑴及本發明之感光性樹 脂組成物(2)之使用方法的形態例,可舉例如調製糊狀之感 光性樹脂組成物’將所得之糊狀感光性樹脂組成物塗佈於石夕 基板上的方法。又,亦可為將使溶解或分散於溶媒中之感光 性樹脂組成物塗佈於發基板上後,將溶媒揮發去除的方法。 又,亦可為將形成於樹脂片材上之薄膜狀感光性樹脂組成物 (接黏薄膜),壓黏於矽基板上的方法等。 此等之中d物狀之感紐細旨組成物(接黏薄膜)的 100110287 66 201140239 方法,係由細微加工性優越之觀點以及將感光性樹脂組成物 層厚度保持為—定的觀點而言屬較佳。 薄膜狀之感光性樹脂組成物(接黏薄膜)的製作方法,可舉 例如以下方法。首先’將本發明之感光性樹脂組成物(1)或 本發明之感光性樹脂組成物(2)於適當之有機溶劑(例如N_ 甲基-2-吡咯啶酮、苯曱醚、甲基乙基酮、甲苯、醋酸乙基 酉曰等)中混合。接著,於成為支撐體之樹脂片材等上進行塗 佈及乾燥,可製成薄膜狀之感光性樹脂組成物(接黏薄膜)。 本發明之感光性樹脂組成物(丨)及本發明之感光性樹脂組 成物(2)係以CMOS影像感測器搭載受光裝置為首,可形成 用於經過對準步驟之半導體裝置製造中的抗銲層。如上述, 其使可見光穿透且硬化物具有抗銲層機能。另,此抗銲層具 有紅外線之遮阻性。 如上述,本發明之感光性樹脂組成物(1)及本發明之感光 性树知組成物(2)係硬化前之感光性樹脂組成物具有可見光 穿透性。藉此,於對準時,可辨識印字於矽基板上之對準記 號。本發明之感光性樹脂組成物(1)及本發明之感光性樹脂 . 組成物(2)係硬化物具有紅外線遮阻性。藉此,於感光性樹 . 脂組成物之硬化後,可防止紅外線由矽基板下面侧進入。 又’本發明之感光性樹脂組成物(1)及本發明之感光性樹俨 組成物(2)係感光性樹脂組成物之硬化物具有抗銲層所需的 性能。具體而言,係具有耐熱性、耐藥品性、絕緣性、耐渴 100110287 67 201140239 性、低曲翹性、對準性。 而且,本發明之感光性樹脂組成物(1)及本發明之感光性 樹脂組成物(2)的可見光穿透性,主要係由鹼可溶性樹脂(A) 之可見光穿透性所決定。因此,鹼可溶性樹脂(A)為使波長 400mn以上且700nm以下之可見光穿透的樹脂。故鹼可溶 性樹脂(A)為不具有吸收400nm以上且7〇〇nm以下之波長之 可見光的官能基或分子構造的樹脂。又,屬於僅具有可進行 對準之程度里之吸收4〇〇nm以上且7〇〇nm以下之波長之可 見光的官能基或分子構造的樹脂。又,驗可溶性樹脂(A)之 分子構造或官能基’係以硬化前之感光性樹脂組成物層之可 見光穿透性中,硬化前之感光性樹脂組成物層之4〇〇nm以 上且700nm以下之可見光穿透率的最大值為5〇%以上之 方法,予以適當選擇。特佳為依70%以上之方式予以適當 選擇。藉此,使硬化前之感光性樹脂組成物之可見光穿透性 為上述下限值以上,則可具有對準步驟中所要求的可見光穿 透性。 本發明之感光性樹脂組成物(1)及本發明之感光性樹脂組 成物(2)係具有使可見光穿透的性質。更具體而言,本發明 之感光性樹脂組成物(1)及本發明之感光性樹脂組成物(2)的 波長400nm以上且700nm以下之可見光穿透率的最大值為 5.0%以上。更佳為10%以上。特佳為15%以上。又,所謂 波長400nm以上且700nm以下之光之穿透率的最大值,係 100110287 68 201140239 指_nm以上且·nm以下之波長_下穿料成為最大 之波長之穿透率的值。藉由上述範圍’於對準時,可辨識印 字於石夕基板下面之對準記號。 尚且,本發明之感光性樹脂組成物(1)及本發明之感光性 樹脂組成物(2)的波長4〇〇nm以上且7〇〇nm以下之可見光穿 透率,係亦考慮其等之硬化物之波長8〇〇nm以上且25〇〇nm 以下之紅外線穿透率,而調整紅外線吸收劑①)之含量等。 具體而言,較佳係如上述般,本發明之感光性樹脂組成物⑴ 及本發明之感光性樹脂組成物(2)的波長4〇〇nm以上且 7〇〇nm以下之可見光穿透率的最大值為5%以上。此外,此 等之硬化物之波長8〇〇nm以上且25〇〇nm以下之紅外線穿透 率的最小值較佳為15%以下。藉此,製造步驟中之對準記 號的辨識性良好1可防止紅外_造成之受光裝置的誤動 作。 本發明之感光性樹脂組成物(1)之硬化物及本發明之感光 性樹脂組成物(2)之硬化物係具有吸收紅外線的性質。更具 體而言,本發明之感光性樹脂組成物(1)之硬化物及本發明 ‘ 之感光性樹脂組成物(2)之硬化物、亦即抗銲層等之保護膜 的最大及收’皮長為波長800nm以上且2500nm以下的範圍 内。 另外’本發明之感光性樹脂組成物(1)之硬化物及本發明 之感光性樹脂組成物(2)之硬化物 的波長800nm以上且 100110287 201140239 2500nm以下之紅外線穿透率的最小值為抓以下。再者, 上述穿透率較佳為1%以上且15%以下,特佳2%以上且1〇% 乂下又波長800nm以上且2500nm以下之紅外線穿透率 的最小值,係在上述波長範圍内成為最大魏波長之穿透率 的值。亦即,所謂波長議⑽以上且250〇nm以下之穿透率 的最小值4 15%以下’係指存在於波長8〇〇nm以上且 2500nm以下之波長範圍中之最大吸收波長之穿透率的值為 15/〇以下。因此,藉由將波長8〇〇nm以上且^⑻nm以下之 、’工外線穿透率的最小值設為上述上限值以下,則因由石夕基板 下面所钕入之紅外光強度充分地變弱,故受光裝置不致發生 誤動作。 本發明之感光性樹脂組成物(丨)及本發明之感光性樹脂組 成物(2)的波長360nm以上且400nm以下之紫外線穿透率的 最小值’較佳為35%以下。特佳為3〇%以下。又,所謂36〇nm 以上且4〇〇nm以下之紫外線穿透率的最小值為35%以下, 係表示360nm以上且400nm以下之波長範圍中之最大吸收 波長的穿透率的值為35%以下。藉此,於曝光步驟中,在照 射屬於紫外線之曝光光時’可使本發明之感光性樹脂組成物 (1)及本發明之感光性樹脂組成物(2)效率佳地反應。 另外,本發明之感光性樹脂組成物(1)之硬化物及本發明 之感光性樹脂組成物(2)之硬化物的絕緣性,為丨〇χ1〇9Ω以 上、較佳為1.0x10 以上。又,絕緣性係於線寬2〇μιη銅 100110287 70 201140239 端子、線間20μιη之基板上,貼附感光性樹脂組成物,使其 依180 C熱硬化5小時後,藉絕緣電阻計(施加1〇ν)所測定 之鄰接銅端子間之絕緣電阻值。因此,可保持各個銲球所搭 載之佈線電路間的絕緣性。 另外,本發明之感光性樹脂組成物(1)之硬化物及本發明 之感光性樹脂組成物(2)之硬化物的耐熱性,係以26〇。匸下之 彈性係數作為指標,260°C下之彈性係數為IMPa以上且 1〇〇〇MPa以下。較佳為3MPa以上且800MPa以下。又,26〇。〇 下之彈性係數係藉動態黏彈性測定裝置(DMA)(頻率: 10Hz,升溫速度:3t/分鐘)所測定之值。藉此,在受光裝 置之將矽基板與電路基板進行銲接的步驟中,可保持矽基板 之剛性。 另外,本發明之感光性樹脂組成物(1)之硬化物及本發明 之感光性樹脂組成物(2)之硬化物,係具有耐助銲劑性。又, 耐助銲劑性、亦即耐藥品性係如下述般進行測定。首先,將 感光性樹脂組成物貼附於半導體晶圓上。接著,依波長 365nm、曝光量700mJ/cm2之條件進行曝光。接著,依 180C、5小時之條件使其熱硬化。其次,將作為銲錫膏之 M34-226C-2Μ〇.8H(千住金屬工業(股)公司製)塗佈於感光 性树知組成物上’藉加熱板依250°C加熱10分鐘使銲錫凝 集。接著,使用屬於助銲.劑洗淨液之PineAlfa ST-1 〇〇〇sx(荒 川化學工業(股)公司製),依7〇°C、1〇分鐘之條件洗淨感光 100110287 71 201140239 性樹脂組成物上之助銲劑。進一步使用純水,依45<t、主 分鐘+25°C、1分鐘之條件進行洗淨。其後,以顯微鏡觀察 感光性樹脂組成物之表面狀態,可測定耐藥品性。如此,籍 由具有咖銲雜,則不朗助銲劑而發生溶解或膨潤。 另外,本發明之感光性樹脂組成物(1)之硬化物及本發明 之感光性樹脂組成物(2)之硬化物的耐濕性,係以吸水率作 為指標’吸水率為5%以下、較佳3%以下。藉此,可防止 佈線電路的腐名虫。 另外,關於本發明之感光性樹脂組成物(1)之硬化物及4 發明之感紐樹脂組成物⑺之硬化物的低輪性,係以楚 璃轉移溫度以下之線膨脹縣α1及室溫下之彈性係數為击 標’ cxl為例如lppm/t以上且細卯心以下。較佳^ 3PPm/t:以上且15Gppm/t:以下。又,室溫之彈性係數为 〇._以上且1GGPa以下。較佳為〇.3GPa以上且8GPa ^ 下。又,玻璃轉移溫度以下之線膨脹係數αΐ係藉 性測定裝置(舰)(模式:㈣,負重:3QmN,H ^ 5C/分鐘)所㈣之值。又,室溫下之彈性係數 彈性測找置(舰)(鮮:_,升溫速度^ 之 測定之值。因此,料使麵轉移溫度訂之線 及室溫下之彈性係數為上述範圍内,可防 置數 以上之本發明之感光性樹月旨 組成物(1)或本發明之感光性 100110287 72 201140239 樹脂組成物(2) ’適合使用作為晶片尺寸之CMOS影像感測 器搭載受光裝置之抗銲層用的感光性樹脂組成物。此種晶片 尺寸之CMOS影像感測器搭載受光裝置係具有搭载了由光 元件所構成之CMOS影像感測器的矽基板、透明基板、規 定該CMOS影像感測器與該透明基板間之間隙的間隔件, 於該矽基板上,設有通孔,藉由形成於該通孔内面之佈線電 路,使該矽基板上面之佈線電路與該矽基板下面之佈線電路 連接,於該石夕基板下面設有抗薛層,使該石夕基板下面之佈線 電路、與電路基板之佈線電路藉銲接予以連接。 另外,本發明之受光裝置的特徵在於:具有搭載了由光元 件所構成之CMOS影像感測器的;&夕基板、透明基板、規定 該CMOS影像感測器與該透明基板間之間隙的間隔件,屬 於於該矽基板上,設有通孔,藉由形成於該通孔内面之佈線 電路,使該矽基板上面之佈線電路與該矽基板下面之佈線電 路連接,於6亥矽基板下面設有抗銲層,使該石夕基板下面之佈 線電路、與電路基板之佈線電路藉銲接所連接的晶片尺寸之 CMOS景>像感測器搭載受光裝置;該抗銲層為本發明之感光 性樹脂組成物(1)之硬化物或本發明之感光性樹脂組成物(2) 之硬化物。 另外,本發明之受光裝置之抗銲層,係藉由將相對於剖面 積,釭外線吸收劑(D)所佔之面積比為〇1%以上且3〇%以下 之薄膜狀感光性樹脂組錢(接黏薄膜)予以層合而形成。上 100110287 73 201140239 述紅外線吸收劑(D)所佔之面積比,較佳為5%以上且30% 以下。於此,抗銲層之剖面積中,所謂紅外線吸收劑(D)所 佔之「面積比」係依例如以下方法所測定。首先,切出藉接 黏薄膜所形成之抗銲層的一部分。接著,非故意地抽出所切 出之部分的一部分,對其剖面進行SEM觀察。其次,觀察 抗銲層中之紅外線吸收劑(D)的粒子。此時,在可辨識粒子 形狀之適當倍率下,將其影像二值化。接著,於上述倍率之 觀察區域内,計算紅外線吸收劑(D)粒子所佔有之面積比。 於不同的剖面中重複此計測數十次,將上述面積比平均化。 如此,得到抗銲層之剖面積中之紅外線吸收劑(D)所佔有的 「面積比」。又,上述面積比之計湏1j方法,適合在紅夕卜線吸 收劑(D)為例如無機粒子的情況下進行計測。 如上述,藉由使紅外線吸收劑(D)所佔有之面積比為上述 下限值以上,則可使波長800nm以上且2500nm以下之紅外 線穿透率的最小值為15%以下。藉此,可抑制紅外線由矽基 板下面側進入,防止受光元件之誤動作。又,藉由使紅外線 吸收劑(D)所佔有之面積比為上述上限值以下,可使波長 400nm以上且700nm以下之可見光穿透率的最大值為5.0% 以上。藉此,於對準時,可辨識印字於矽基板下面的對準記 號。 (實施例) 以下,根據實施例及比較例詳細說明本發明,但本發明並 100110287 74 201140239 不限定於此。在下述實施例及比較财,說明麟形成受光 裝置等之抗銲層的接黏薄膜的作成例。 (實施例1) 1·將具有驗可雜基及雙鍵讀脂(可藉光及熱之雙方進行 硬化的硬化雜脂:甲基㈣酸減質物A㈣祕清 漆树月曰· MPN)之合成雙盼a㉟酉分酸清漆樹脂 LF-4871 ’大日本油墨化學公司製)之固形份6〇%mek溶液 5〇〇g,投入至2L燒瓶中。㈣,於其中添加作為觸媒之三 丁基胺1.5g、及作為聚合禁止劑之氫醌〇 15g,加溫至 100 C。於其中,依30分鐘滴下環氧丙基甲基丙烯酸酯 180.9g’以l〇〇C攪拌反應5小時。藉此,得到不揮發份74〇/〇 之曱基丙烯酸基改質雙酚A型酚醛清漆樹脂(MPN)(曱基丙 烯酸基改質率50%)。 2.樹脂清漆之調製 將作為鹼可溶性樹脂(A)之上述曱基丙烯酸基改質雙酚A 型盼紛酸清漆樹脂(MPN) 5 7. 〇重量%、作為光聚合起始劑之 IRGACURE651(Ciba Specialty Chemicals(股)公司製)3.0 重 量%、參酚型環氧樹脂E1032H60(Japan Epoxy Resin(股)公 司製)33.0重量%、作為酚樹脂之酚酚醛清漆型樹脂 PR53467(住友BAKEUTE(股)公司製)4.0重量%、與作為紅 外線吸收劑之硼化鑭LaB6-F(日本新金屬(股)公司製)3.0重 量% ’溶解於曱基乙基酮(MEK,大伸化學公司製)中,得到 100110287 75 201140239 樹脂清漆。又’紅外線吸收劑之硼化鑭LaB6-F係藉由依嚴 格條件予以破碎而形成。 3.接黏薄膜之調製 將上述樹脂清漆以刮刀塗佈機塗佈至支撐基材聚酯薄膜 (帝人杜邦薄膜(股)公司製,RL-07,厚38μιη),以7(TC乾燥 10分鐘,得到膜厚20μιη之接黏薄膜。 (實施例2) 將作為驗可溶性樹脂(Α)之上述曱基丙烯酸基改質雙酚A 型酚酚醛清漆樹脂(MPN) 43.0重量%、作為丙烯酸樹脂之三 羥曱基丙烷三曱基丙烯酸酯LIGHT ESTER TMP(共榮社化 學(股)公司製)12.0重量%、作為光聚合起始劑(B)之 IRGACURE651(Ciba Specialty Chemicals(股)公司製)3.0 重 量%、參齡型環氧樹脂E1032H60(Japan Epoxy Resin(股)公 司製)33.0重量%、作為酚樹脂之酚酚醛清漆型樹脂 PR53467(住友BAKELITE(股)公司製)4.0重量%、與作為紅 外線吸收劑之硼化鑭LaB6-F(日本新金屬(股)公司製)5.0重 量% ’溶解於曱基乙基酮(MEK,大伸化學公司製)中,得到 樹脂清漆。接黏薄膜之調製係與實施例1同樣地進行。又’ 與實施例1相同地,紅外線吸收劑之硼化鑭LaB6-F係藉由 依嚴格條件予以破碎而形成。 (實施例3)
將作為鹼可溶性樹脂(A)之上述曱基丙烯酸基改質雙酚A 100110287 76 201140239 型酚酚醛清漆樹脂(MPN) 42.0重量%、作為丙烯酸樹脂之三 羥甲基丙烷三曱基丙烯酸酯LIGHT ESTER TMP(共榮社化 學(股)公司製)12.0重量%、作為具有酚性羥基與羧基之化合 物的二酚酸(東京化成工業(股)公司製〇重量%、作為光聚 合起始劑(B)之 IRGACURE651(Ciba Specialty Chemicals(股) 公司製)3.0重量%、參酚型環氧樹脂E1032H60(Japan Epoxy Resin(股)公司製)33.0重量%、作為酚樹脂之酚酚醛清漆型 樹脂PR53467(住友BAKELITE(股)公司製)4.0重量%、與作 為紅外線吸收劑之硼化鑭LaB6-F(日本新金屬(股)公司 製)5.0重量% ’溶解於甲基乙基酮(MEK,大伸化學公司製) 中,得到樹脂清漆。接黏薄膜之調製係與實施例1同樣地進 行。又’與實施例1相同地,紅外線吸收劑之硼化鑭LaB6-F 係藉由依嚴格條件予以破碎而形成。 (實施例4) 除了將作為丙烯酸樹脂之三羥曱基丙烧三曱基丙烯酸酯 LIGHT ESTER TMP(共榮社化學(股)公司製)之調配量由 12.0重量份變更為1〇.〇重量份,將硼化鑭LaB6_F(日本新金 屬(股)公司製)之調配量由5.0重量。/〇變更為7.0重量%以 外,其餘與實施例2同樣地進行樹脂清漆之調製、接黏薄膜 之調製。又,與實施例2相同地,紅外線吸收劑之棚化鑭 LaB6-F係藉由依嚴格條件予以破碎而形成。 (實施例5) 100110287 77 201140239 除了將曱基丙烯酸基改質雙酚A型酚酚醛清漆樹脂(MPN) 之調配量由43.0重量%變更為45.0重量%,又,取代硼化 鑭LaB6-F(曰本新金屬(股)公司製)5.〇重量%而使用酞菁系 化合物EXCOLOR910(曰本觸媒(股)公司製)3.〇重量%作為 紅外線吸收劑以外,其餘與實施例2同樣地進行樹脂清漆之 調製、接黏薄膜之調製。 (實施例6) 除了取代酜菁系化合物EXCOLOR910(日本觸媒(股)公司 製)3.0重量%而使用酞菁系化合物exc〇L〇R906(曰本觸媒 (股)公司製)3.0重量°/❶作為紅外線吸收劑以外,其餘與實施 例5同樣地進行樹脂清漆之調製、接黏薄臈之調製。 (實施例7) 除了將曱基丙烯酸基改質雙酌· A型紛紛酸清漆樹脂(mpn) 之調配量由43.0重量%變更為42.0重量%,又,將硼化綱 LaB6-F(曰本新金屬(股)公司製)5 〇重量。/〇變更為二銨系化 合物KAYASORB IRG-068(曰本化藥(股)公司製)6 〇重量% 以作為紅外線吸收劑以外,其餘與實施例2同樣地進行樹脂 清漆之s周製、接黏薄膜之調製。又,與實施例2相同地,紅 外線吸收劑之硼化鑭LaB6-F係藉由依嚴格條件予以破碎而 形成。 (實施例8) 除了將硼化鑭LaB6-F(日本新金屬(股)公司製)6 〇重量% 100110287 78 201140239 變更為錫摻雜氧化名itq伞、古r 一 # & 刹、0 IT〇 h末(二遂材料電子化成(股)公司 …量%以作為紅外線吸收劑以外,其餘與實施例7同 樣地進仃樹脂凊漆之調製、接黏㈣之簡。又,與實施例 7相同地’紅外線吸收劑之靴鑭£抓^係藉由依嚴格條 件予以破碎而形成。 (實施例9) 除了將硼化鑭LaB6_F(日本新金屬(股)公司製)6 〇重量% 變更為錄摻雜氧化豸#電性粉末τ](三菱材料電子化成 (股)公司製)6.G重量%以作為紅外線吸收劑以外,其餘與實 施例7同樣地進行樹脂清漆之調製、接黏薄膜之調製。又, 紅外線吸收劑之銻摻雜氧化錫導電性粉末T-1係藉由依嚴 格條件予以破碎而形成。 (實施例10) 除了將作為鹼可溶性樹脂(A)之酚酚醛清漆樹脂S_3(住友 BAKELITE(股)公司製)54·0重量%、作為環氧樹脂之矽改質 環氧樹脂ΒΥ16-115(東麗道康寧聚矽氧(股)公司製)29.〇重 量份、取代光聚合起始劑(Β)而使用作為光酸產生劑(c)之下 式所示之參酚與二疊氮萘醌的磺酸酯9.0重量%、與作為紅 外線吸收劑之硼化鑭LaB6-F(日本新金屬(股)公司製)8.〇重 量%,溶解於曱基乙基酮(MEK,大伸化學公司製)中,得到 樹脂清漆以外,接黏薄膜之調製係與實施例1同樣地進行。 又’與實施例1相同地,紅外線吸收劑之棚化鑭LaB6-F係 100110287 79 201140239 件料破碎而形成。 [化 27]
(式中Φ、Q2、Q3之
(比較例1) 除了將作為鹼可溶性樹脂(A)之上述甲基丙烯酸基改質雙 酚A型酚酚醛清漆樹脂(MPN) 45.0重量%、作為丙烯酸樹 脂之三羥甲基丙烷三曱基丙烯酸酯LIGHT ESTER TMP(共 榮社化學(股)公司製)12.0重量%、作為光聚合起始劑之 IRGACURE651(Ciba Specialty Chemicals(股)公司製)3.0 重 量%、參盼型環氧樹脂E1032H60(Japan Epoxy Resin(股)公 司製)35.0重量%、與作為酚樹脂之酚酚醛清漆型樹脂 PR53467(住友BAKELITE(股)公司製)5.〇重量%,溶解於曱 基乙基酮(MEK ’大伸化學公司製)中,得到樹脂清漆以外, 其餘與實施例1同樣地進行接黏薄膜之調製。 1.穿透率評價 各實施例及比較例所得之接黏薄膜,係藉分光光度計 (UV-3100PC,島津製作所公司製)測定穿透率。於此,將波 長400nm以上且700nm以下之穿透率成為最大之波長及此 時之穿透率設為最大穿透率。又,將波長36〇nm以上且 100110287 80 201140239 40〇nm以下之穿透率成為最小之波長(最大吸收波長)及此 時之穿透率設為穿透率⑴。又,將波長800nm以上且25〇〇nm - 以下之穿透率成為最小之波長(最大吸收波長)及此時之穿 透率設為穿透率(ii)。 2.絕緣性評價 將各實施例及比較例所得之接黏薄膜,如下述般評價絕緣 性。首先’將各實施例及比較例所得之接黏薄膜,貼附於線 寬20μιη銅端子、線間20μηι之基板上。接著,依波長: 365nm、曝光量:700mJ/cm2之條件進行曝光。再依i8〇t>c、 5小時之條件使接黏薄膜熱硬化。其後,藉絕緣電阻計(施 加ΙΟν),測定10點之鄰接銅端子間之絕緣電阻值。接著, 將其平均值作為各接黏薄膜的測定值。 3.25°C及260°C下之彈性係數 各實施例及比較例所得之接黏薄膜,係、如下述般評價彈性 係數。將各實施例及比較例所得之接黏薄膜,依波長: 365nm、曝光量:700mJ/cm2之條件進行曝光。再依18〇艺、 5小時之條件進行熱硬化。接著,藉動態黏彈性測定裝置 * (DMA),依頻率H升溫速度:rc/分鐘之條件測定貯 *藏彈性係數。分別測定2宂及靴下之貯藏彈性係數。 4.耐助銲劑性 各實施例及比較例所得之接黏薄膜 銲劑性。先將各實施例及比較例所得之接黏薄膜貼附二半導 100110287 81 201140239 體晶圓上。接著,依波長:365nm、曝光量:700mJ/cm2之 條件進打曝光。再依180Ϊ、5小時之條件使接黏薄膜熱硬 化。接著,於接黏薄膜上塗佈作為銲錫膏之 M34-226C-21-10.8H(千住金屬工業(股)公司製)。接著,藉加 熱板以250°C加熱1〇分鐘使銲錫凝集。其次,使用屬於助 銲劑洗淨液之PineAlfa ST-1000SX(荒川化學工業(股)公司 製),依70 C、1 〇分知之條件洗淨接黏薄膜上之助銲劑。再 使用純水,依45°C、1分鐘+25°c、1分鐘之條件進行洗淨。 其後’以顯微鏡確s忍接黏溥膜之表面狀態。如下述,將接黏 薄膜之表面狀態視為財助銲劑性而以〇χ進行評價。 〇:於藥液處理前後未見到表面狀態差異 X :藥液處理前後,在表面上觀察到皺紋、膨潤。 5.吸水率評價 各實施例及比較例所得之接黏薄膜,係如下述般評價吸水 率。首先’將各實施例及比較例所得之接黏薄膜,使用設定 為60°C之層合機予以貼合。接著,製作膜厚ι〇〇μιη之接黏 薄膜。其次’依波長:365nm、曝光量:7〇〇mJ/cm2之條件 進行曝光。再依180°C、5小時之條件使接黏薄膜熱硬化。 將所得之熱硬化後之接黏薄膜粉碎為約5mm正方。接著, 精秤約10mg作為測定樣本。接著’將測定樣本依85。(:熱處 理10分鐘。再精秤測定樣本之重量,將此時之重量設為a。 另一方面,將測定樣本依85°C、85%、1〇分鐘進行濕熱處 100110287 82 201140239 理。接著,精秤濕熱處理後之重量,將此時之重量設為b。 吸水率係藉下式算出。 • 吸水率(%)=((b-a)/a)xl00 ’ 6.平均線膨脹係數αΐ 將各實施例及比較例所得之接黏薄臈,依波長:365nm、 曝光量:700mJ/cm2之條件進行曝光。再依18〇。匚、5小時 之條件進行熱硬化,製作測定樣本。使用所得之測定樣本, 藉熱機械特性測定裝置(TMA)(模式:拉伸,負重:3〇mN, 昇溫速度:5°C/分鐘)測定線膨脹係數。此時,將環境溫度 為〇°C至30°C之平均線膨脹係數作為測定值。 7.面積比 將各實施例及比較例所得之接黏薄膜,切出作為讓觀 察用樣本。接著’非故意地抽出所切出之部分的—部分,對 其剖面進行SEM觀察。其次,觀察樣本中之紅外線吸收劑 P)的粒子。此時’在可辨識粒子形狀之適當倍率下,將其 影像二值化。接著,於上述倍率之觀察區域内,計算紅外線 及收劑(D)粒子所伯有之面積比。於不同的剖面中重複此計 •測數十次’將上述面積比平均化。表2、表3中之「面積比」, •係指該經平均化之值。又,表2、表3中之實_ 5〜7,係 因紅外線吸收劑⑼為有機物,而溶解於溶媒(甲基乙基酮) 中。因此,實施例5〜7無法計測出面積比。 100110287 83 201140239 鬥1<】 分解溫度(°c) 2715以上 250-350 250-350 210 982以上 656以上 最大吸收波長(nm) 1100 966 1100 1500 2200 紅外線吸收劑 曰本新金屬(股) 曰本觸媒(股) 曰本觸媒(股) 曰本化藥(股) 三菱材料電子化成(股) 三菱材料電子化成(股) LaB6-F EXCOLOR910 EXCOLOR906 KAYASORBIRG-068 ITO粉末 導電性粉末T-1 硼化鑭 酞菁系化合物 酞菁系化合物 二銨系化合物 錫摻雜氧化銦 銻摻雜氧化錫 寸8 SSI sol 201140239 v〇 45.0 | 33.0 I 12.0 q 100.0 400 26.4 S ^r Ο *rj ,100以上 <N 〇 m oi N.D. 45.0 33.0 12.0 ρ 100.0 〇 | 31.6 I S m Ο σ! ro i 100以上 (N 〇 m <N N.D. 實施例4 43.0 33.0 10.0 q 对’ 〇 100.0 〇 \〇 vS s fn o ! 1400 ro ,100以上 fN 〇 <N (N s 28.4 4£) ♦ζ 42.0 I 33.0 | 12.0 o — ρ 100.0 〇 〇4 s co 1 1300 00 ,100以上 <N 〇 m CN s (N 卜· <N m 43.0 33.0 12.0 ! o — 100.0 400 〇〇 1 1 s v〇 vd 1400 On 100以上 (N 〇 oi 岑 Λ&) 57.0 j 33.0 p 100.0 〇 16.4 s Os ;1100 10.2 ,100以上 (N 〇 H U0 S 1 0Q 1 | §3 _ g W «4 § C/3 Έ I ί 1 0 8 S 鞭 I i 東京化成工業(股) § •4 tn S? 1 ? tn 雲 ¥ ξ m Η S m 8 iP,m1 rp〇r 案 § -Ο ί rpnr t π| •\L〇 <0 1 ιιφί 1 ί 韻· 1 ιιφί I 1 | ±1 ξ s 举 卜 P 1? 1 BftL ?R Ρ 1 对助銲劑性 g 發 z·™·' I a g Jj V§ MPN001 S E1032H60 BY16415 1RGACURE651 LIGHT ESTER TMP PR53647 二酚酸 LaB6-F EXCOLOR910 EXCOLOR906 1 KAYASORBIRG-068 ΓΓΟ粉末 導電性粉末T-l 最大穿透率(l)(400nm~700nm) 1 最小穿透率(2)(360nm^400nm) 最小穿透率(3)(800nm〜2500nm) < 装 ¢-¾ 祕清雜脂 1 1 1 參盼與二疊氮萘酿之確酸醋 DC vea 键 € B- »-丨'1 酚祕清雜脂 4,4’ -雙(對經基苯基)戊酸 硼侧 -ϋ 神C 酞菁系化合物 1 Ί S $ 1 銻獅氧祕 鹼可溶-蝴脂 環賴脂 光聚合起始劑 丨光Stt生劑 i)d I mm 紅外線吸收劑 評價結果
s s ASSUOOI 20 4 〔s 比較你卜 45.0 ^ | 35.0 12.0 I ο wS 100.0 馨 g m 27.8 1 I 85.4 | 100以上 CN 〇 ο ο I 54.0 29.0 § § 100.0 1 oo S m 3 1400 Ο) 100以上 CN 〇 N (N 實施例9 42.0 33.0 12.0 p ^r § 100.0 1 66.8 s m 1 32.8 1 2200 CO U〇〇以上1 <N 艺 〇 (N fN (N οό 00 42.0 33.0 Li2.〇 I p § 100.0 1 1 79.2 1 s ro 1500 m ο 100以上 (N 〇 <Ί cs 沄 s 卜 雀 42.0 ,33.0 12.0 o 寸· § 100.0 1 1 Π·6 1 s ΓΠ 1100 cn I 100以上 CS 〇 (N <N I NX). | I I g % § 1 I § I *®4 S? 1 1 ί 8 S 鞭 I 8 麵 Η 帕 h®4 § m 8 ¥ σι S ¥ 1 m 8 1 m 養 ί 实 $ 'Ί S? 5 AM 'Ί I 1 Ιΐφί g 1 Ιΐφί 2 ▲ 1 111^ I 蝴· a # 1 Μ 1 豳 卜 。。 5Q 1 e〇L PS w 卜 P s (N 财助鮮劑性 g 蝴· 〇 P s "b 1 雲 g ii ! MPN001 ,E1032H60 ΒΥ16-115 IRGACURE651 LIGHT ESTER TMP PR53647 g 1 LaB6-F EXCOLOR910 EXCOLOR906 KAYASORBIRG-068 ΓΓ0粉末 導電性粉末T-l 最大穿透率(lX400nm~700nm) 最小穿透率⑵(360miWK)0nm) 最小穿透率(3X800nm~2500nm) < id 祕貪雜脂 1 矽改質環氧樹脂 1 參紛與二疊氮萘脇之墙酸酯 um 1 泼 ve 一 ft- B- 墩 i'l 細脂 i4 ψ 硼化鋼 1 A3 酞菁系化合物 丨二敍系化合物 錫摻雜氧化麵 錄摻雜氧麟 驗可溶働脂 1 w 驾 1 i)位 蓮 m 1酴樹脂 1 Ο k il 紅外線吸收劑 評債結果 900
卜 830 ISO I 201140239 (結果) 如表3所示,比較例中,因不含紅外線吸收劑(D),故8〇〇nm 以上且2500nm以下之波長光之最小穿透率為85 4%之較大 " 值。在使用此比較例之接黏薄膜的情況,因為由矽基板下側 面穿透抗銲層所進入的紅外線,而受光元件發生誤動作。 另一方面,如表2、表3所示般,使用了本發明之含有紅 外線吸收劑(D)之感光性樹脂組成物的實施例丨〜⑺中,波長 800nm以上且2500nm以下之紅外線穿透率的最小值為 15%以下。又,上述實施例卜忉中,波長4〇〇nm以上且7〇〇nm 以下之可見光穿透率的最大值為5%以上。又,上述實施例 1〜10中,波長360nm以上且400nm以下之紫外線穿透率的 最小值為35%以下。此外’上述實施例ι〜1()中,耐熱性、 絕緣性、彈性係數、耐助銲劑性、吸水率、平均線膨脹係數、 面積比率均為所需特性或範圍内。 (受光裝置) 依下述步驟製作受光裝置。首先,如圖12般準備具有形 成至銅佈線電路之受光元件的矽基板。接著,於該石夕美板之 下面側,壓黏實施例4之接黏薄膜。其次,藉由曝光及顯影, • 於搭載銲球之部分上形成開口部。接著,對接黏薄膜進行加 熱硬化,形成接銲劑。其次,藉由銲接至電路基板之佈線電 路,而製作受光裝置。此受光裝置因紅外線之遮光性良好, 故受光元件不致發生誤動作,可穩定動作。 100110287 87 201140239 (產業上之可利用性) 根據本發明’以業性效率佳且廉價製造_雜紅外線 由石夕基板下面側進人之半導體裝置、尤其是受光裝置。因 此,可工紐效率佳且廉㈣造陳外_造叙誤動作少 的半導體裝置、尤其是受光裝置。 本申請案係主張以2010年3月26曰申請之曰本申請案特 願2010-072255號為基礎的優先權,其揭示内容全部引用至 此。 【圖式簡單說明】 圖1為銲接方式之CMOS影像感測器搭戴受光裝置之概 略剖面圖。 圖2為表示銲接方式之CMOS影像感測器搭載受光^置 之製造步驟的概略剖面圖。 圖3為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖4為表示銲接方式之CMOS影像感測器搭载受光裝置 之製造步驟的概略剖面圖。 置 置 置 圖5為表示銲接方式之CMOS影像感測器搭載受光裝 之製造步驟的概略剖面圖。 & 圖6為表示銲接方式之CMOS影像感測器搭載受光襄 之製造步驟的概略剖面圖。 & 圖7為表示鋅接方式之CMOS影像感㈣搭载受光震 100110287 88 201140239 之製造步驟的概略剖面圖。 圖8為表示銲接方式之CMOS影像感測器搭載受光裝置 • 之製造步驟的概略剖面圖。 ' 圖9為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖10為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖11為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖12為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖13為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖14為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 圖15為表示銲接方式之CMOS影像感測器搭載受光裝置 之製造步驟的概略剖面圖。 . 圖16為表示銲接方式之CMOS影像感測器搭載受光裝置 4 之製造步驟的概略剖面圖。 圖17為表示個片化步驟的概略剖面圖。 【主要元件符號說明】 受光裝置 100110287 89 201140239 2 電路基板 3 透明基板 4 間隔件 4a 間隔件用感光性樹脂組成物層 5 間隙 6 矽基板 8 受光部 9 銲錫 10 通孔 11 上面 12 下面 15 佈線電路 16 電極墊 17 絕緣膜 18 通孔 19 絕緣膜 20 阻蔽層 21 鑛銅層 22 佈線電路 23 感光性樹脂組成物層 24 感光性樹脂組成物層 25 抗鲜層 100110287 90 201140239 26 銲球搭載部分 27 鲜球 30 多數受光裝置於平面方向上相連者 - 33 遮罩 34 紫外線 35 接合體 40 砍基板 100110287 91
Claims (1)
- 201140239 七、申請專利範圍: 1. 一種感光性樹脂組成物,其特徵為含有· 鹼可溶性樹脂(A); 光聚合起始劑(B);與 最大吸收波長為800nm以上且2500ηιη以下之範圍内的紅 外線吸收劑(D); 波長400nm以上且700nm以下之玎見光穿透率的最大值 為5.0%以上。 2. —種感光性樹脂組成物,其特徵為含有. 鹼可溶性樹脂(A); 光酸產生劑(C);與 最大吸收波長為800nm以上且2500nm以下之範圍内的紅 外線吸收劑(D); 波長400nm以上且700nm以下之$見光穿透率的最大值 為5.0%以上。 3. 如申請專利範圍第1或2項之感光性樹脂組成物,其 中,波長3 60nm以上且400nm以下之糸外線穿透率的最小 值為35%以下。 4. 如申請專利範圍第1或2項之感光性樹脂組成物,其 中,上述感光性樹脂組成物的硬化物之波長800nm以上且 2500nm以下之紅外線穿透率的最小值為15%以下。 5. 如申請專利範圍第i或2項之感光性樹脂組成物,其 100110287 92 201140239 中’紅外線吸收劑(D)之熱分解溫度為200°C以上。 . 6.如申請專利範圍第1或2項之感光性樹脂組成物,其 • 中’紅外線吸收劑(D)為金屬蝴化物、氧化鈦' 氧化結、锡 才多雜氧化銦、錄換雜氧化錫、偶I化合物、胺鑽 化合物、亞胺鏽(iminium)化合物、蒽醌化合物、花青化合 物、一叙(diimonium)化合物、方酸(squarylium)化合物、駄 %化合物、秦菁化合物、蒽酿i(anthraquinone)化合物、萘酉昆 化合物、二硫醇化合物、聚曱炔(p〇lymethine)化合物中之1 種以上。 7. 如申請專利範圍第1或2項之感光性樹脂組成物,其 中,含有0.01重量%以上且15重量%以下之紅外線吸收劑 (D)。 8. 如申請專利範g)第丨或2項之感光性樹脂組成物,其 中,紅外線吸收劑(D)之平均粒徑為1〇μιη以下。 9. 如申切專利圍第1或2項之感光性樹脂組成物,其 中,進一步含有具酚性羥基與羧基之化合物(E)。 10. 如申凊專利I。圍第1或2項之感光性樹脂組成物,其 甲’具雜減與絲之化合物(E)之全部或—部分為下述 •—般式(22)、(23)及⑽中之任-者所示的化合物; [化1] 100110287 93 (22) 201140239(23) HOOC—— _ _ [化2] • HOOC—— c [化3] HOOC(24) (其中,a、b、e及f為1〜3之整數’ c及d為1〜5之整數, 又,R21、R22為芳香族以外之有機基)。 11·如申請專利範圍第1或2項之感光性樹脂組成物,其 中,具酚性羥基與羧基之化合物(E)之重量平均分子量為ι〇〇 以上且5000以下。 12. 如申請專利範圍第1或2項之感光性樹脂組成物,其 中’進一步含有熱硬化性樹脂(F)。 13. 如申請專利範圍第12項之感光性樹脂組成物,其中, 熱硬化性樹脂(F)為環氧樹脂。 14. 如申請專利範圍第13項之感光性樹脂組成物,其中, 上述衣氧树月曰之全部或—部分為酚酚醛清漆型環氧樹脂、甲 ⑽駿清漆型環氧樹脂、二環戍二烯型環氧樹脂及參紛甲婉 100110287 94 201140239 型環氧樹脂中之1種以上。 15. 如申請專利範圍第1或2項之感光性樹脂組成物,其 中,進一步含有光聚合性化合物(G)。 16. 如申請專利範圍第1或2項之感光性樹脂組成物,其 中’驗可溶性樹脂(A)係具有光聚合性雙鍵且具有鹼可溶性 基的驗可溶性樹脂。 17 ·如申睛專利範圍第1或2項之感光性樹脂組成物,其 中,鹼可溶性樹脂(A)為(曱基)丙烯醯基改質酚樹脂。 18.如申請專利範圍第1或2項之感光性樹脂組成物,其 係晶片尺寸之CMOS影像感測器搭載受光裝置之抗銲層用 的感光性樹脂組成物; 該晶片尺寸之CMOS影像感測器搭载受光裝置係具有: 搭載著由光元件所構成之CMOS影像感測器之矽基板; 透明基板;與 規定上述CMOS影像感測器與上述透明基板間之間隙的 間隔件; 上述矽基板係設有通孔; 藉由形成於上述通孔内面之佈線電路,使上述矽基板上面 之佈線電路與上述石夕基板下面之佈線電路連接. 於上述石夕基板下面係設有上述抗銲層; 使上述碎基板下面之佈線電路、與電路基板之佈線電路藉 銲接而連接。 9 100110287 95 201140239 19. 一種受光裝置’其特徵為屬於下述之晶片尺寸之 CMOS影像感測器搭裁受光裝置;其具有: 搭載著由光元件所構成之CMOS影像感測器之矽基板; 透明基板;與 規定上述CMOS影像感測器與上述透明基板間之間隙的 間隔件; 上述石夕基板係設有通孔; 藉由形成於上述通孔内面之佈線電路,使上述矽基板上面 之佈線電路與上述石夕基板下面之佈線電路連接; 於上述矽基板下面係設有抗銲層; 使上述石夕基板下面之佈線電路、與電路基板之佈線電路藉 銲接而連接; 9 上述抗銲層係申請專利範圍第項之感光性樹脂組成 物的硬化物。 20. 如申請專利範圍第19項之受光裝置’其中,上述抗銲 層係相對於剖面積,紅外線吸收劑(D)所佔有之面積比為 0.1%以上且30%以下,並藉由將由_狀之上述感光_ 脂組成物所構成之接黏薄膜進行壓黏而形成者。 100110287 96
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