TW201000550A - Protective film composition for wafer dicing - Google Patents

Protective film composition for wafer dicing Download PDF

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Publication number
TW201000550A
TW201000550A TW98117363A TW98117363A TW201000550A TW 201000550 A TW201000550 A TW 201000550A TW 98117363 A TW98117363 A TW 98117363A TW 98117363 A TW98117363 A TW 98117363A TW 201000550 A TW201000550 A TW 201000550A
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Taiwan
Prior art keywords
protective film
group
water
film composition
wafer
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TW98117363A
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Chinese (zh)
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TWI399402B (en
Inventor
Kyong-Ho Lee
Gi-Jin Kwun
Shi-Jin Sung
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Dongwoo Fine Chem Co Ltd
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Priority claimed from KR1020080050260A external-priority patent/KR101539762B1/en
Priority claimed from KR1020080050261A external-priority patent/KR101539763B1/en
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Publication of TW201000550A publication Critical patent/TW201000550A/en
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Publication of TWI399402B publication Critical patent/TWI399402B/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L37/00—Compositions of homopolymers or 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 a heterocyclic ring containing oxygen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Dicing (AREA)

Abstract

Disclosed is a protective film composition for wafer dicing, comprising at least one resin selected from the group consisting of polyethyloxazoline and polyvinylpyrrolidone, at least one component selected from the group consisting of a water-soluble resin and an alcoholic monomer, and a solvent, such as water or a mixture of water and an organic solvent.

Description

201000550 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種具軔 物，係用於半導體切割製^好熱穩疋性之保護膜組成 【先前技術】 在半導體裝置製程中，曰由丨 成社制.· τ日日51切割製程後係為半導體 i之為二二m:naT pr°cess)，如此可藉由沿著其之間被 稱之為街道(Street)之邊界區切割晶 置分離。切割製程後則勃耔曰y制^ 句叹置之褒 σ 傻則執仃晶片製程，即完成半導體產 品0 隨著半導體裝置整合度增加，街道寬度隨之變窄，201000550 VI. Description of the Invention: [Technical Field] The present invention relates to a protective film composition for semiconductor cutting, which is good for thermal stability. [Prior Art] In the manufacturing process of a semiconductor device,丨成社制制.. τ日日51 cutting process is the semiconductor i is two or two m: naT pr°cess), so by the boundary zone between them called Street The cutting crystal is separated. After the cutting process, the burgundy y system ^ sighs and sighs σ silly is the wafer process, that is, the semiconductor product is completed 0. As the integration degree of the semiconductor device increases, the street width becomes narrower.

St:械性質亦跟著變差。因此，晶圓切割製程係 不斷被改變以解決上述問題。 裝置整合度的增加，將可能使層板最上層位置之絕 緣膜内的主要材料聚醯亞胺(pGlyimide)於晶圓切割製程 過程中破裂或損害。因此，晶圓切割製程從利用刀片切 割晶圓’改為先用雷射貫穿晶圓再用刀片㈣晶圓。此 外’僅使用雷射切割晶圓之製程亦可執行。然而，使用 雷射之雷射切割製程中’由於雷射的熱度可能產生煙霧 且煙霧四散，因而造成晶圓上表面遭受汙染的問題。 已知用於解決此問題之技術係包括將水溶性樹脂如 聚乙烯醇、聚乙二醇或纖維素運用於晶圓表面以形成保 遵膜’然後再放射雷射光之製程方法。 201000550 。j而即使使用此方法，因雷射光的熱度可能使晶 圓之切割表面產切氣體，而使晶圓之保護臈發生不良 ^層°料’煙霧可沿著魏體產生，而累積於分層狀 悲的保濩膜與晶圓的上表面之間。當接著用水沖洗晶圓 的保護膜時，此煙霧沉義將無法去除，㈣ 陷。 水溶性樹脂具有不好之熱穩定性。因此，雷射晶圓 切割製程中雷射照射後將產生内熱，水溶性樹脂如聚乙 烯醇將受此熱而熱解。此外，熱解期間可能發生交聯反 應’於雷射晶圓切割製程後，所產生之交聯材料即使用 水沖洗也無法去除，仍保留在晶圓上表面。 目前，典型的雷射晶圓切割製程包括用雷射貫穿晶 圓’再用刀片切割晶圓。針對利用刀片晶圓切割，若晶 圓之保護膜具有高硬度，則保護膜可能會破裂，而使晶 圓切割所產生的不純物可能滲人破裂膜的空隙。因此些 非水溶性不純物貼附於晶圓上表面，其並無法藉由水^ 洗掉而成為缺陷。 【發明内容】 技術問顳 有鑑於上述習知技藝之問題，本發明之一目的就是 在提供-種用於晶圓切割之保護膜組成物，其具有高熱 ?疋性’因此可防止切割製程中因雷射照射而產生熱解 又聯材料，且對晶圓具有高黏著力，因此可防止雷射晶 201000550 圓切割製程中保護膜的分層（delamination)，以及可形成 具有適當硬度之保護膜，使保護膜即使晶圓經雷射穿孔 再用刀片切割仍不會破裂。 技術解決 本發明提供一種用於晶圓切割之保護膜組成物，包 括至少一選自聚乙基°惡0坐琳（polyethyloxazoline)及聚乙 埽°比略烧酮（polyvinylpyrrolidone)所組成之群組之樹 月曰、至少一選自水溶性樹脂（water_s〇luble resin)及酒精性 單體（alcoholic monomer)所組成之群組之成分、以及一溶 劑’例如水或水與有機溶劑之混合物。 優點敎荔 根據本發明’用於晶圓切割之保護膜組成物具有高 熱穩定性’可防止因切割製程中雷射照射而產生熱解交 聯材料’且對B曰圓顯示高黏著力（a(JheSiVeneSS)，因此可 防止雷射晶圓切割製程中保護膜的分層。再者’使用保 瘦膜組成物可形成具適當硬度之保護膜，因此使晶圓切 割時’保護膜並不會有破裂的問題。此外，因保護膜組 成物對晶圓具有較高的適用性（applicability)，其可被廣 泛應用於具有整合度增加之半導體裝置製造期間之切割 製程。 【實施方式】 201000550 最佳模式 本發明指出一種用於晶圓切割之保護膜組成物，包 括至少一選自聚乙基噁唑啉及聚乙烯吡咯烷酮所組成之 群組之樹脂、至少一選自水溶性樹脂及酒精性單體所組 成之群組之成分、以及一溶劑，例如水或水與有機溶劑 之混合物。 本發明之保護膜組成物中，其至少一選自聚乙基喔 坐'#及t乙稀吼嘻烧g同所組成之群組之樹脂，以及至少 一選自水溶性樹脂及酒精性單體所組成之群組之成分之 重1比可為1 : 9〜7 : 3，且溶劑可包含於組成物之總黏 度設於10-100 cP之範圍内。 用於晶圓切割之保護膜組成物可根據組成物之樹脂 成分的總重量，進一步包括1〇〜8〇 ppm之水溶性界面活 性劑。 用於晶圓切割之一般保護膜組成物的樹脂成分之實 方€*例包括例如聚乙烯醇（p〇lyvinyl alc〇h〇i，ΡΆ)、聚乙二 1 (polyethylene giycol，PEG)及纖維素等樹脂以及例如 聚丙烯酸(p〇lyacrylic acid，PAA)等水溶性樹脂。其中， 具有，基或敌基之水溶性樹脂係具有耐熱差或因熱解而 產生交聯副產物之問題。然而，當水溶性樹枝用於本發 明之組成物，聚乙基噁唑啉及聚乙烯吡咯烷酮具有較好 的熱穩定性且高水溶度。 本發明之保護膜組成物較佳係包括聚乙基噁唑啉或 聚乙基噁唑啉與聚乙烯吡咯烷酮之混合物，作為至少一 201000550 選自聚乙基"ϋ#及聚乙料所組成之群組之樹 脂。 已知聚乙基噁唑啉之一例子係商品名為Aquaz〇1之 聚（2-乙基-2-喔〇坐琳）（poly(2_ethyl_2_〇xaz〇line))，具有高 水溶度且較好的熱穩定性。當使賴重分㈣（tga)於 氮氣環境中以每分鐘1〇t:加熱速度測量重量減輕率 (weight reduction)，其重量減輕開始發生在35〇它或較 高，且於約3阶發生劇烈分解。然而，分解過程不合 產生交聯副產物，因此不會形成不溶於水之缺陷。 聚乙稀吼錢酮亦具有高水溶度與較好的熱穩定 性。^使用TGA於氮氣環境中以每分鐘阶之加熱速 度測篁重罝減輕率，其重量減輕開始發生於3〇〇艺且於 約40(TC發生劇烈分解。然:而，分解過程不會產生交聯 副產物，所以不會形成不溶於水之缺陷。 醇、二乙二醇、三乙二醇、四乙二醇、丙二醇 醇、環己二甲醇、異戊四醇、三甲基丙醇等。 本發明之保護膜組成物中，其至少—選自水溶性樹 月旨，酒精性單體所組成之群組之成分用於提高保護膜對 基板之黏著力及調整保賴之硬度。水溶性樹脂的例子 包括聚乙烯醇、聚乙二醇(咖）、聚丙二醇(PPG)、纖維 素、聚丙烯酸(PAA)等’而酒精性單體的例子包括 ® 拿、一r — a：含 一一一 卞 一 環己 性樹脂之聚乙_本身具有高度水溶性且則 圓有極好的黏著力。因此，當使料乙稀醇時，可辦力 用於晶圓切割之保護膜組成物的黏著力， ： 201000550 照射後保護膜的分層。另外，關於聚乙烯醇，其溶解後 之水溶度與儲存穩定性（storage stability)之變化與其皂 化度（degree of saponification)及分子量有關。若聚乙稀 醇之皂化度為1〇〇%，則聚乙烯醇具有不好的水溶度且於 溶解於水後形成凝體（gel)，因而其黏度隨時間增加。因 此，可使用皂化度為87-90%之聚乙烯醇。因皂化度為 87-90%之聚乙烯醇並不會隨時間改變黏度，可用於作為 溶劑。此外，聚乙烯醇之溶解度與穩定度隨時間之變化 與其分子量有關。當聚乙烯醇之聚合度（degree of polymerization)為500〜2000時，其溶解度與穩定度車交 佳。因此，本發明較佳是使用具87-90%皂化度與 500〜2000聚合度之聚乙烯醇。 然而，因為聚乙烯醇具有不好的熱穩定性’所以其 使用係為混有具較高熱穩定性之聚乙基噁唑啉及/或聚 乙烯吡咯烷酮之混合物形式，且係於25CTC或低於250°C 下且不會產生不溶於水之交聯副產物之範圍内。 本發明之保護膜組成物中，其至少一選自聚乙基噁 唑啉及聚乙烯吡咯烷酮所組成之群組之樹脂，以及至少 一選自水溶性樹脂及酒精性單體所組成之群組之成分之 重量比可為1 : 9〜7 : 3，較佳為3 : 7〜7 : 3。當這些成分 使用上述範圍時，其熱穩定性、對晶圓之黏著力及保護 膜之硬度係證明如所預期的。 本發明之保護膜組成物中，水溶性表面活性劑扮演 著提升組成物適用性與增加儲存穩定性之角色。 201000550 一般用於雷射晶圓切割製程之保護膜可具有1μηι或 更厚之厚度。如果保護膜組成物之適用性太差，晶圓的 中心與其邊緣之薄膜厚度將出現差異，因而降低製程邊 限（process margin)。因此，本發明之保護膜組成物中係 添加水溶性界面活性劑以因而提高組成物之適用性。水 溶性界面活性劑之例子包括聚醚修飾烧基石夕氧燒 (polyether modified alkylsiloxane)、聚醚修飾聚烷基石夕氧 烧（polyalkylsiloxane)、具經基(hydroxyl group)之聚_修 飾聚二甲基石夕氧院(polydimethylsiloxane)、具經基之聚趟 -聚酯（polyether-polyester)修飾聚烷基矽氧烷、非離子聚 丙烯水溶性界面活性劑（non-ionic polyacrylic water-soluble surfactant)、醇烷氧基化物（aic〇h〇l alkoxylate)及高分子含氟水溶性界面活性劑 (fluorine-based water-soluble surfactant)，其可單獨使用 或為其二或多個之組合。 再者，本發明人發現水溶性界面活性劑於保護膜組 成物中係扮演作為分散劑的角色，使保護膜組成物不會 隨時間而形成膠體之事實。因此，本發明之保護膜組成 物可增加適用性與咼儲存穩定性係由於水溶性界面活性 劑的利用。 本發明之保護膜組成物中，依據保護膜組成物之樹 脂成分的總重量’水溶性界面活性劑之用量可為1〇〜8〇 ppm。當水溶性界面活性劑使用上迷範圍時，保護膜組 成物包括適用性與儲存穩定性之性質會變得很好，且熱 穩定性、對晶圓之黏著力及保護膜之硬度亦可改善。， 201000550 本發明之保護膜組成物中，溶劑為水。或者，為增 加保護膜組成物之薄膜厚度或提升其適用性，所使用溶 劑可為水與有機溶劑之混合物形式。有機溶劑的例子包 括異丙醇（isopropylalcohol)、丙二醇單甲基醚醋酸酯 (propyleneglycolmonomethylether acetate, PGMEA)、丙二 醇單曱基醚（propyleneglycolmonomethylether, PGME)及 碳酸烧基酯（alkyl carbonate)，例如礙酸丁浠醋、碳酸丙 烯醋、丙三醇碳酸醋（glycerine carbonate)或碳酸乙烯 酯。此些有機溶劑可單獨使用或為其二或多個之組合。 丙二醇單甲基醚本身具有高互溶性，甚至與水之任 何混合比都可溶於水。然而，丙二醇單甲基醚醋酸酯每 100公克的水具有16公克或更少之溶解度’所以必須使 用上述範圍。 特別地，以具有高極性之碳酸烷基酯如碳酸丁烯 酯、碳酸丙烯酯、丙三醇碳酸酯或碳酸乙烯酯作為有機 溶劑的事例中，可適宜地改善儲存穩定度與適用性。 碳酸乙烯酯於室溫下為固體’但可適當地溶解於水 中，而且丙三醇碳酸酯可以任何混合比溶解於水中。然 而，碳酸丁烯酯及碳酸丙烯酯於室温下之水溶度分別為 10%及25%或更少，因此須使用上述範圍。 本發明之保護膜組成物中’添加溶劑以使保護祺組 成物之總黏度設為10〜100 cP。如果保護膜組成物之黏度 落於上述範圍内’可顯示較好的適用性’且可獲得之詞· 晶圓的黏著力及保護膜的硬度係如預期的。 201000550 為了改善性能，本發明之保護膜組成物可進一步包 括至少一先前技術已知之添加物。 尤其，用於晶圓切割之保互模組成物可更包括用於 抑制溶劑發泡之去泡洙劑，且去泡沫劑之例子包括聚矽 氧燒（polysiloxane)、聚烧基石夕氧院、氟石夕酮（fluorosilicone) 聚合物等。 此外，本發明可針對於利用用於晶圓切割之保護膜 組成物製造之半導體裝置。本發明之半導體裝置即使當 使用雷射或刀片切割晶圓時，仍可完全由保護膜所保 護’且由於保護膜易於清洗而可使其製造不具有缺陷。 本發明將藉由下述說明但並非解釋為限制本發明之 實施例以得到更好的理解。 實施例1〜1〇及比較例1〜6:用於晶圓切割之保護膜 組成物的製備 實施例1 將5公克聚乙基嗔π坐淋（Aquazol，聚合度（DP) : 50) 與5公克聚乙烯醇（PVA) (DP: 500,皂化度（DS): 87〜90%) 加入裝配有攪拌器之混合器内，且加入水作為溶劑，使 溶液黏度為60 cp。於室溫且5〇〇 rpm下攪拌1小時後， 即製備出用於晶圓切割之保護膜組成物。 201000550 實施例2 將3公克聚乙基σ惡唾琳（Aquazol，DP : 50)，3公克 聚乙烯吡咯烷酮（DP : 1200)與4公克PVA (DP : 1700， DS : 87〜90%)加入裝配有攪拌器之混合器内，且加入水 作為溶劑，使溶液黏度為60 cP。於室溫且500 rpm下攪 拌1小時後，即製備出用於晶圓切割之保護膜組成物。 實施例3 將3公克聚乙基噁唑啉（Aquazo卜DP : 50)，3公克 聚乙烯吡咯烷酮（DP : 1200)與4公克PVA (DP : 1700， DS : 87〜90%)加入裝配有攪拌器之混合器内，且加入 70/30 (w/w)比率之水與丙二醇單曱基醚（PGME)之混合 物作為溶劑，使溶液黏度為60 cP。於室溫且500 rpm下 攪拌1小時後，即製備出用於晶圓切割之保護膜組成物。 實施例4 將7公克聚乙基0惡嗤琳（Aquazol，DP : 500)與3公 克PVA(DP : 500，DS : 87〜90%)加入裝配有攪拌器之混 合器内，且加入70/30 (w/w)比率之水與PGME之混合物 作為溶劑，使溶液黏度為60 cP。於室溫且500 rpm下攪 拌1小時後，即製備出用於晶圓切割之保護膜組成物。 實施例5 12 201000550 將3公克聚乙基嗯嗤琳（入911&2〇1，〇?:500)與7公 克PVA (DP : 1700，DS : 87〜90%)加入裝配有授拌器之 混合器内’且加入70/30 (w/w)比率之水與PGME之混合 物作為溶劑’使溶液黏度為60 cP。於室溫且5〇〇 rpm下 攪拌1小時後，即製備出用於晶圓切割之保護膜組成物。 實施例6 將5公克聚乙基鳴嗤琳（Aquazol，DP : 50)與5公克 PVA (DP : 500，DS : 87〜90%)加入裝配有攪拌器之混合 器内，且依據聚乙基噁唑啉與PVA之總重量分別加入3〇 ppm之界面活性劑（BYK-337，自BYK取得）與去泡沐劑 (BYK-025 ’自BYK取得）’以及加入水作為溶劑，使溶 液黏度為60 cP。於室溫且500 rpm下授拌1小時後，即 製備出用於晶圓切割之保護膜組成物。 實施例7 將3公克聚乙基°惡哇琳（Aquazol，DP : 50)，3公克 聚乙烯吡咯烷酮（DP : 1200)與4公克PVA (DP : 1700， DS : 87〜90%)加入裝配有擾拌器之混合器内，且依據聚 乙基β惡唾琳、聚乙烯°比11各烧酮與PVA之總重量分別加入 30卩!)111之界面活性劑作丫1^337，自3丫1^取得）與去泡沐 劑（ΒΥΚ-025 ’自ΒΥΚ取得），以及加入水作為溶劑，使 溶液黏度為60 cP。於室溫且500 rpm下授拌1小時後， 即製備出用於晶圓切割之保護膜組成物。 201000550 實施例8 將2公克聚乙基"惡嗤琳（Aquazol，DP : 50)，2公克 聚乙烯吡咯烷酮（DP : 1200)與6公克PVA (DP : 17〇〇， DS : 87〜90%)加入裝配有攪拌器之混合器内，且依據聚 乙基°惡°坐琳、聚乙烯°比p各烧酮與P VA之總重量分別加入 30??111之界面活性劑（3丫1^337，自3丫1^取得）與去泡沐 劑（BYK-025，自BYK取得），以及加入水作為溶劑，使 溶液黏度為60 cP。於室溫且500 rpm下擾拌1小時後， 即製備出用於晶圓切割之保護膜組成物。 實施例9 將7公克聚乙基噁嗤琳（Aquazol，DP : 500)與3公 克PVA(DP : 500，DS : 87〜90%)加入裝配有授拌器之混 合器内，且依據聚乙基噁唑啉與PVA之總重量分別加入 30卩口111之界面活性劑^丫1!1-337，自6丫1^取得）與去泡沫 劑（BYK-025，自BYK取得），以及加入水作為溶劑，使 溶液黏度為60 cP。於室溫且500 rpm下攪拌1小時後， 即製備出用於晶圓切割之保護膜組成物。 實施例10 將3公克聚乙基噁唑啉（Aquazol，DP : 500)，7公克 PVA (DP : 1700，DS : 87〜90%)，1 公克三甘醇 14 201000550 (tdethyleneglycol，TEG)與 0.3 公克碳酸 丁烯酯（butylene carbonate)加入裝配有攪拌器之混合器内，且依據聚乙基 11惡唾淋與PVA之總重量分別加入3〇 之界面活性劑 (BYK-337，自BYK取得）與去泡沫劑（Βγκ_〇25，自byk 取得）’以及加入水作為溶劑’使溶液黏度為6〇 cP。於 至溫且500 rpm下攪拌1小時後，即製備出用於晶圓切 割之保遵膜組成物。 比較例1 將10公克PVA(DP : 1700，DS : 87〜90%)加入裝配 有攪拌器之混合器内，且加入水作為溶劑，使溶液黏度 為60 CP。於室溫且500 rpm下攪拌1小時後，即製備出 用於晶圓切割之保護膜組成物。 比較例2 將 9 公克 PVA (DP : 1700，DS : 87〜90%)與 1 公克 聚乙二醇（pEG)(重量平均分子量：700)加入裝配有攪拌 器之混合器内，且加入水作為溶劑，使溶液黏度為60 CP。於室溫且500 rpm下攪拌1小時後，即製備出用於 晶圓切割之保護膜組成物。 比較例3 將 9 公克 pvA (DP : 170〇，DS : 87〜90%)與 1 公克 15 201000550 異戊四醇（pentaerythritol)加入裝配有授拌器之混合器 内，且加入70/30 (w/w)比率之水與PGME之混合物作為 溶劑，使溶液黏度為60 cP。於室溫且500 rpm下攪拌1 小時後，即製備出用於晶圓切割之保護膜組成物。 比較例4 將 8 公克 PVA (DP : 1700，DS : 87〜90%)，1 公克 PEG (重量平均分子量：700)與1公克異戊四醇加入裝配 有授拌器之混合器内，且加入70/30 (w/w)比率之水與 PGME之混合物作為溶劑，使溶液黏度為60 cP。於室溫 且500 rpm下授拌1小時後，即製備出用於晶圓切割之 保護膜組成物。 比較例5 將 9 公克 PVA (DP : 1700，DS : 87〜90%)與 1 公克 PEG (重量平均分子量：700)加入裝配有攪拌器之混合器 内’且依據PVA與PEG之總重量加入300 ppm之界面 活性劑（BYK-337 ’自BYK取得），且加入水作為溶劑， 使溶液黏度為60 cP。於室溫且500 rpm下擾拌1小時 後，即製備出用於晶圓切割之保護膜組成物。 比較例6 將 9 公克 PVA (DP : 1700，DS : 87〜90%)與 1 公克 16 201000550 異戊四醇加入裝配有攪拌器之混合器内，且依據PVA與 異戊四醇之總重量加入300 ppm之界面活性劑 (BYK-337 ’自BYK取得）’且加入70/30 (w/w)比率之水 與PGME之混合物作為溶劑，使溶液黏度為60 cP。於 室溫且500 rpm下攪拌1小時後，即製備出用於晶圓切 割之保護膜組成物。 測試實例1 :去除率(Strip Rate)之測量 將實施例與比較例的每一樣本藉由旋轉塗佈（spin coating)塗佈於4英吋大小之氧化矽基板上，且調整轉速 (rpm)使所得之薄膜於ll〇°C乾燥15分鐘後具有Ιμιη厚 度，因而形成保護膜。利用DRM測量去除水中之保護 膜的速率。測量單位以每秒移除之薄膜厚度表示之。測 試結果如下面表一所示。 ◎ : 1000 nm/s 或更多 〇 :介於800與少於1000 nm/s之間 △:介於500與少於800 nm/s之間 x :少於 500 nm/s 測試實例2:適用性之測量 將實施例與比較例的每一樣本藉由旋轉塗佈塗佈於 4英吋大小之氧化矽基板上，且調整轉速（rpm)使所得之 薄膜於11(TC乾燥15分鐘後具有Ιμιη厚度’因而形成保 17 201000550 護膜。之後，測量晶圓中心及與晶圓中心間隔2公分與 4公分距離之所有方向的位置之薄膜厚度，且決定其標 準差，因而評估出保護膜組成物之適用性。測試結果如 下面表一所示。 ◎ : 1%或更少 〇：超過1 %但不多於2% △:超過2%但不多於4% X :超過4% 測試實例3 :錯筆硬度(Pencil Hardness)之測量 將實施例與比較例的每一樣本藉由旋轉塗佈塗佈於 4英叶大小之氧化砍基板上，且調整轉速（rpm)使所得之 薄膜於ll〇°C乾燥15分鐘後具有Ιμιη厚度，因而形成保 護膜。之後，根據HD D 0202測量保護膜對鉛筆的硬度。 測試結果如下面表一所示。 測試實例4 :黏著力之測量 將實施例與比較例的每一樣本藉由旋轉塗佈塗佈於 4英叶大小之氧化硬基板上，且調整轉速（rpm)使所得之 薄膜於11CTC乾燥15分鐘後具有Ιμιη厚度，因而形成保 護膜。之後，根據JIS Κ5600-5-6執行橫切（cross-cut)測 試（捲尺測量測試（taping tast))。測試結果如下面表一所 示。 18 201000550 ◎:分離晶格（detached lattices)數目（0) 〇:分離晶格數目（介於1與少於5之間） △:分離晶格數目（介於5與少於10之間） X :分離晶格數目（10或更多） 測試實例5 :熱穩定性之測量 將實施例與比較例的每一樣本藉由旋轉塗佈塗佈於 4英忖大小之氧化石夕基板上，且調整轉速（rpm)使所得之 薄膜於110°C乾燥15分鐘後具有Ιμιη厚度，因而形成保 護膜。之後，將保護膜置於250°C熱空氣烘箱10分鐘， 然後檢查其是否被水沖洗掉，以確認不溶於水之熱解交 聯材料是否受熱產生。測試結果如下面表一所示。 ◎:完全剝離態（stripped state) 〇 :存在微粒子（fine particles) △:存在大量未剝離(non-stripped)部分 x :未剝離態 測試實例6 :儲存穩定性之測量 將實施例與比較例的樣本儲存於室溫，每週測量其 黏性與適用性，以檢查性質是否隨時間改變。測試結果 如下面表一所示。 ◎:穩定達36週或更久 19 201000550 〇 :穩定達18週或更久 △:穩定達8週或更久 X :穩定低於8週 表一 去除率 適用性 鉛筆 硬度 黏著力 熱穩定性 儲存 穩定性 實施例1 ◎ ◎ 7H ◎ ◎ 〇 實施例2 ◎ 〇 9H 〇 ◎ 〇 實施例3 ◎ 〇 9H 〇 ◎ 〇 實施例4 ◎ ◎ 7H ◎ ◎ 〇 實施例5 ◎ ◎ 7H ◎ ◎ 〇 實施例6 ◎ ◎ 9H 〇 ◎ ◎ 實施例7 ◎ ◎ 7H ◎ ◎ ◎ 實施例8 ◎ ◎ 9H ◎ 〇 ◎ 實施例9 ◎ ◎ 7H 〇 ◎ ◎ 實施例1 ◎ ◎ 5H ◎ ◎ ◎ 比較例1 Δ X 9H ◎ Δ 〇 比較例2 〇 ◎ Η X Δ 〇 比較例3 Δ 〇 Η X Δ 〇 比較例4 〇 〇 Η X Δ Δ 比較例5 〇 ◎ Η X Δ 〇 比較例6 Δ 〇 Η X Δ Δ 以上所述僅為舉例性，而非為限制性者。任何未脫 離本發明之精神與範疇，而對其進行之等效修改或變 更，均應包含於後附之申請專利範圍中。 20 201000550 【圖式簡單說明】 無 【主要元件符號說明】St: The mechanical properties are also getting worse. Therefore, the wafer dicing process is constantly being changed to solve the above problems. The increased integration of the device will likely cause the pGlyimide, the main material in the insulating film at the uppermost layer of the laminate, to rupture or damage during the wafer dicing process. Therefore, the wafer dicing process is changed from using a blade to cut a wafer to a laser through a wafer and then a blade (four). In addition, the process of using only laser-cut wafers can be performed. However, in the laser cutting process using a laser, the surface of the wafer is contaminated due to the possibility that the heat of the laser may generate smoke and the smoke is scattered. Techniques known to solve this problem include a process for applying a water-soluble resin such as polyvinyl alcohol, polyethylene glycol or cellulose to the surface of a wafer to form a film which is then irradiated with laser light. 201000550. j Even if this method is used, the heat of the laser light may cause the cutting surface of the wafer to produce a gas, and the protection of the wafer may be bad. The smoke may be generated along the Wei body and accumulated in the layer. A sad film between the film and the upper surface of the wafer. This smog will not be removed when the wafer's protective film is subsequently rinsed with water, (4). Water-soluble resins have poor thermal stability. Therefore, internal heat is generated after laser irradiation in a laser wafer cutting process, and a water-soluble resin such as polyvinyl alcohol is thermally decomposed by this heat. In addition, cross-linking reactions may occur during pyrolysis. After the laser wafer cutting process, the resulting cross-linked material, which is rinsed with water, cannot be removed and remains on the upper surface of the wafer. Currently, a typical laser wafer dicing process involves the use of a laser through the wafer to re-cut the wafer. For the cutting using the blade wafer, if the protective film of the crystal has a high hardness, the protective film may be broken, and the impurities generated by the crystal cutting may infiltrate the void of the ruptured film. Therefore, some water-insoluble impurities are attached to the upper surface of the wafer, and they cannot be washed away by water to become defects. SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, it is an object of the present invention to provide a protective film composition for wafer dicing which has high heat enthalpy' and thus prevents the cutting process from being The pyrolysis and the bonding material are generated by the laser irradiation, and have high adhesion to the wafer, thereby preventing delamination of the protective film in the laser crystal 201000550 circular cutting process, and forming a protective film having appropriate hardness. So that the protective film will not break even if the wafer is laser-perforated and then cut with a blade. Technical Solution The present invention provides a protective film composition for wafer dicing, comprising at least one group selected from the group consisting of polyethyloxazoline and polyvinylpyrrolidone. The sapphire, at least one component selected from the group consisting of water-soluble resin and alcoholic monomer, and a solvent such as water or a mixture of water and an organic solvent. Advantages 敎荔 According to the invention, the protective film composition for wafer cutting has high thermal stability, which prevents pyrolysis of the crosslinked material due to laser irradiation in the cutting process and exhibits high adhesion to the B circle (a (JheSiVeneSS), therefore, it can prevent the delamination of the protective film in the laser wafer cutting process. In addition, 'the thin film composition can be used to form a protective film with appropriate hardness, so the 'protective film will not be cut when the wafer is cut. There is a problem of cracking. In addition, since the protective film composition has high applicability to the wafer, it can be widely applied to a cutting process during the manufacture of a semiconductor device having an increased degree of integration. [Embodiment] 201000550 The present invention indicates a protective film composition for wafer dicing, comprising at least one resin selected from the group consisting of polyethyloxazoline and polyvinylpyrrolidone, at least one selected from the group consisting of water-soluble resins and alcoholicity. a component of the group consisting of monomers, and a solvent such as water or a mixture of water and an organic solvent. At least one selected from the group consisting of the protective film composition of the present invention. The resin of the group consisting of ethyl hydrazine and the group of at least one selected from the group consisting of water-soluble resins and alcoholic monomers may have a weight ratio of 1 : 9 to 7 : 3 , and the solvent may be included in the composition, and the total viscosity is set in the range of 10 to 100 cP. The protective film composition for wafer cutting may further include the total weight of the resin component of the composition, further including 1〇~8〇ppm water-soluble surfactant. The resin composition of the general protective film composition for wafer cutting includes, for example, polyvinyl alcohol (p〇lyvinyl alc〇h〇i, ΡΆ) a resin such as polyethylene giycol (PEG) or cellulose, and a water-soluble resin such as polyacrylic acid (PAA), wherein the water-soluble resin having a base or an enemy group has poor heat resistance or A problem of cross-linking by-products due to pyrolysis. However, when water-soluble branches are used in the composition of the present invention, polyethyloxazoline and polyvinylpyrrolidone have good thermal stability and high water solubility. Preferably, the protective film composition comprises polyethyl acetonate a mixture of porphyrin or polyethyloxazoline and polyvinylpyrrolidone as a resin of at least 201000550 selected from the group consisting of polyethyl phthalocyanine and polyethyl amide. One of polyethyloxazolines is known. The example is a poly(2-ethyl-2-〇xaz〇line) product of the name Aquaz〇1, which has high water solubility and good thermal stability. The weight fraction (4) (tga) was measured in a nitrogen atmosphere at a rate of 1 〇t: heating rate per minute, and the weight loss began to occur at 35 〇 or higher, and violent decomposition occurred at about 3 orders. However, the decomposition process does not produce cross-linking by-products, and thus does not form a defect of being insoluble in water. Polyvinyl ketone also has high water solubility and good thermal stability. ^ Using TGA to measure the rate of light reduction in the nitrogen atmosphere at a heating rate per minute, the weight loss begins to occur at 3 〇〇 and at about 40 (TC undergoes violent decomposition. However: the decomposition process does not occur Cross-linking by-products, so it does not form a defect that is insoluble in water. Alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol alcohol, cyclohexanedimethanol, pentaerythritol, trimethylpropanol The protective film composition of the present invention is at least selected from the group consisting of water-soluble trees, and the components of the group consisting of alcoholic monomers are used to improve the adhesion of the protective film to the substrate and to adjust the hardness of the substrate. Examples of the water-soluble resin include polyvinyl alcohol, polyethylene glycol (coffee), polypropylene glycol (PPG), cellulose, polyacrylic acid (PAA), etc., and examples of the alcoholic monomer include ®, a r - a: Polyethylene _ containing one-to-one-one-cyclohexene resin itself is highly water-soluble and has excellent adhesion to the circle. Therefore, when the ethylene glycol is used, the composition of the protective film for wafer cutting can be made. Adhesion of the material, : 201000550 Layering of the protective film after irradiation. Regarding polyvinyl alcohol, the change in water solubility and storage stability after dissolution is related to its degree of saponification and molecular weight. If the degree of saponification of polyvinyl alcohol is 1%, Vinyl alcohol has a poor water solubility and forms a gel after dissolving in water, so its viscosity increases with time. Therefore, polyvinyl alcohol having a degree of saponification of 87 to 90% can be used. The degree of saponification is 87- 90% of polyvinyl alcohol does not change viscosity over time and can be used as a solvent. In addition, the solubility and stability of polyvinyl alcohol change with time is related to its molecular weight. When the degree of polymerization of polyvinyl alcohol is When it is 500 to 2000, its solubility and stability are good. Therefore, the present invention preferably uses polyvinyl alcohol having a degree of saponification of 87 to 90% and a polymerization degree of 500 to 2000. However, since polyvinyl alcohol has a bad Thermal stability' so it is used in the form of a mixture of polyethyloxazoline and/or polyvinylpyrrolidone with high thermal stability, and is at 25 CTC or below and does not produce insoluble Within the scope of the cross-linked by-products, the protective film composition of the present invention, at least one selected from the group consisting of polyethyloxazoline and polyvinylpyrrolidone, and at least one selected from the group consisting of water-soluble resins and The weight ratio of the components of the group consisting of alcoholic monomers may be 1: 9 to 7: 3, preferably 3: 7 to 7: 3. When these components use the above range, their thermal stability, crystal orientation The adhesion of the circle and the hardness of the protective film are as expected. In the protective film composition of the present invention, the water-soluble surfactant plays a role in enhancing the suitability of the composition and increasing the storage stability. The protective film for the wafer cutting process may have a thickness of 1 μm or more. If the applicability of the protective film composition is too poor, the film thickness at the center of the wafer and its edge will be different, thus reducing the process margin. Therefore, a water-soluble surfactant is added to the protective film composition of the present invention to thereby improve the suitability of the composition. Examples of the water-soluble surfactant include a polyether modified alkylsiloxane, a polyether modified polyalkylsiloxane, and a poly-modified polydimethyl group having a hydroxyl group. Polydimethylsiloxane, polyether-polyester modified polyalkyl siloxane, non-ionic polyacrylic water-soluble surfactant, An alkoxylate (aic 〇h〇l alkoxylate) and a polymer-based water-soluble surfactant, which may be used singly or in combination of two or more thereof. Further, the inventors have found that the water-soluble surfactant acts as a dispersing agent in the protective film composition, so that the protective film composition does not form a colloid over time. Therefore, the protective film composition of the present invention can increase the applicability and the storage stability of the ruthenium due to the utilization of the water-soluble surfactant. In the protective film composition of the present invention, the amount of the water-soluble surfactant may be from 1 〇 to 8 〇 ppm, based on the total weight of the resin component of the protective film composition. When the water-soluble surfactant is used in the above range, the properties of the protective film composition including applicability and storage stability become good, and the thermal stability, the adhesion to the wafer, and the hardness of the protective film can also be improved. . , 201000550 In the protective film composition of the present invention, the solvent is water. Alternatively, in order to increase the film thickness of the protective film composition or to improve the applicability thereof, the solvent used may be in the form of a mixture of water and an organic solvent. Examples of the organic solvent include isopropylalcohol, propylene glycol monomethyl ether acetate (PMMEA), propylene glycol monomethyl ether (PGME), and alkyl carbonate, such as diced acid浠 vinegar, propylene carbonate, glycerine carbonate or ethylene carbonate. These organic solvents may be used singly or in combination of two or more thereof. Propylene glycol monomethyl ether itself has high mutual solubility and is soluble in water even in any mixing ratio with water. However, propylene glycol monomethyl ether acetate has a solubility of 16 grams or less per 100 grams of water', so the above range must be used. Particularly, in the case of an alkyl carbonate having a high polarity such as butylene carbonate, propylene carbonate, glycerin carbonate or ethylene carbonate as an organic solvent, storage stability and suitability can be suitably improved. The ethylene carbonate is a solid at room temperature but can be suitably dissolved in water, and the glycerol carbonate can be dissolved in water at any mixing ratio. However, the water solubility of butylene carbonate and propylene carbonate at room temperature is 10% and 25% or less, respectively, and therefore the above range must be used. In the protective film composition of the present invention, a solvent is added to set the total viscosity of the protective ruthenium composition to 10 to 100 cP. If the viscosity of the protective film composition falls within the above range, 'good applicability' can be exhibited and the available words· the adhesion of the wafer and the hardness of the protective film are as expected. 201000550 In order to improve performance, the protective film composition of the present invention may further comprise at least one additive known in the prior art. In particular, the die-cut composition for wafer dicing may further include a defoaming agent for suppressing solvent foaming, and examples of the defoaming agent include polysiloxane, poly sinter , fluorosilicone polymer, and the like. Furthermore, the present invention is directed to a semiconductor device fabricated using a protective film composition for wafer dicing. The semiconductor device of the present invention can be completely protected by the protective film even when the wafer is cut using a laser or a blade and can be made without defects due to the easy cleaning of the protective film. The invention is to be understood by the following description, but not by way of limitation. Examples 1 to 1 and Comparative Examples 1 to 6: Preparation of protective film composition for wafer dicing Example 1 5 g of polyethyl 嗔 π sitting (Aquazol, degree of polymerization (DP): 50) and 5 g of polyvinyl alcohol (PVA) (DP: 500, degree of saponification (DS): 87 to 90%) was placed in a mixer equipped with a stirrer, and water was added as a solvent to make the solution viscosity 60 cp. After stirring at room temperature and 5 rpm for 1 hour, a protective film composition for wafer dicing was prepared. 201000550 Example 2 3 g of polyethyl sigma (Aquazol, DP: 50), 3 g of polyvinylpyrrolidone (DP: 1200) and 4 g of PVA (DP: 1700, DS: 87 to 90%) were added to the assembly. In a mixer with a stirrer, water was added as a solvent to make the solution viscosity 60 cP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Example 3 3 g of polyethyloxazoline (Aquazo Bu DP: 50), 3 g of polyvinylpyrrolidone (DP: 1200) and 4 g of PVA (DP: 1700, DS: 87-90%) were added and stirred. In a mixer of the apparatus, a mixture of 70/30 (w/w) ratio of water and propylene glycol monodecyl ether (PGME) was added as a solvent to make the solution viscosity 60 cP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Example 4 7 g of polyethyl oxalate (Aquazol, DP: 500) and 3 g of PVA (DP: 500, DS: 87 to 90%) were placed in a mixer equipped with a stirrer, and 70/ was added. A mixture of 30 (w/w) ratio of water and PGME was used as a solvent to give a solution viscosity of 60 cP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Example 5 12 201000550 3 gram of polyethyl eucalyptus (into 911 & 2〇1, 〇?: 500) and 7 gram of PVA (DP: 1700, DS: 87 to 90%) were added to the mixer equipped with a mixer Add a 70/30 (w/w) ratio of water to PGME as a solvent in the mixer to make the solution viscosity 60 cP. After stirring at room temperature and 5 rpm for 1 hour, a protective film composition for wafer dicing was prepared. Example 6 5 g of polyethyl phthalocyanine (Aquazol, DP: 50) and 5 g of PVA (DP: 500, DS: 87 to 90%) were placed in a mixer equipped with a stirrer, and based on polyethyl 3 〇ppm of surfactant (BYK-337, obtained from BYK) and defoaming agent (BYK-025 'obtained from BYK) were added to the total weight of oxazoline and PVA, respectively, and water was added as a solvent to make the solution viscosity. It is 60 cP. After the mixture was stirred at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Example 7 3 g of polyethyl ethoxylate (Aquazol, DP: 50), 3 g of polyvinylpyrrolidone (DP: 1200) and 4 g of PVA (DP: 1700, DS: 87 to 90%) were added to the assembly. In the mixer of the scrambler, according to the total weight of the polyethyl β 恶 琳 、, polyethylene ratio of 11 ketone and PVA, respectively, 30 卩!) 111 surfactant is used as 丫1^337, from 3丫1^ obtained) and defoaming agent (ΒΥΚ-025 'self-acquisition), and adding water as a solvent to make the solution viscosity 60 cP. After the mixture was stirred at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. 201000550 Example 8 2 g of polyethyl "Aquazol (DP: 50), 2 g of polyvinylpyrrolidone (DP: 1200) and 6 g of PVA (DP: 17 〇〇, DS: 87 to 90%) Adding a mixer equipped with a stirrer, and adding 30??111 of surfactant (3丫1) according to the total weight of the polyethyl ketone, polyethylene ratio, and each of the ketone and P VA ^337, obtained from 3丫1^) and defoaming agent (BYK-025, obtained from BYK), and adding water as a solvent to make the solution viscosity 60 cP. After being scrambled for 1 hour at room temperature and at 500 rpm, a protective film composition for wafer dicing was prepared. Example 9 7 g of polyethyl acesulfame (Aquazol, DP: 500) and 3 g of PVA (DP: 500, DS: 87 to 90%) were added to a mixer equipped with a stirrer, and according to polyethyl b. The total weight of the oxazoline and PVA was added to 30 mouthwash 111 surfactants 丫1!1-337, obtained from 6丫1^) and defoamer (BYK-025, obtained from BYK), and added Water was used as a solvent to make the solution viscosity 60 cP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer dicing was prepared. Example 10 3 g of polyethyloxazoline (Aquazol, DP: 500), 7 g of PVA (DP: 1700, DS: 87 to 90%), 1 g of triethylene glycol 14 201000550 (tdethyleneglycol, TEG) and 0.3 Add butylene carbonate to a mixer equipped with a stirrer, and add 3 界面 of surfactant (BYK-337, obtained from BYK) according to the total weight of polyethyl 11 sputum and PVA. With a defoamer (Βγκ_〇25, obtained from byk) and adding water as a solvent, the solution has a viscosity of 6〇cP. After stirring at a temperature of 500 rpm for 1 hour, a film-forming composition for wafer cutting was prepared. Comparative Example 1 10 g of PVA (DP: 1700, DS: 87 to 90%) was placed in a mixer equipped with a stirrer, and water was added as a solvent to make the solution viscosity 60 C. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Comparative Example 2 9 g of PVA (DP: 1700, DS: 87 to 90%) and 1 g of polyethylene glycol (pEG) (weight average molecular weight: 700) were placed in a mixer equipped with a stirrer, and water was added thereto. Solvent to make the solution viscosity 60 CP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Comparative Example 3 9 g of pvA (DP: 170 Å, DS: 87 to 90%) and 1 gram of 15 201000 550 pentaerythritol were added to a mixer equipped with a stirrer, and 70/30 (w) was added. /w) A mixture of water and PGME as a solvent to give a solution viscosity of 60 cP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Comparative Example 4 8 g of PVA (DP: 1700, DS: 87 to 90%), 1 g of PEG (weight average molecular weight: 700) and 1 g of pentaerythritol were added to a mixer equipped with a stirrer, and added. A mixture of 70/30 (w/w) ratio of water and PGME was used as a solvent to make the solution viscosity 60 cP. After the mixture was stirred at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Comparative Example 5 9 g of PVA (DP: 1700, DS: 87 to 90%) and 1 g of PEG (weight average molecular weight: 700) were added to a mixer equipped with a stirrer' and added to 300 based on the total weight of PVA and PEG. Peptide surfactant (BYK-337 'obtained from BYK), and water was added as a solvent to make the solution viscosity 60 cP. After the scramble was stirred at room temperature and 500 rpm for 1 hour, a protective film composition for wafer dicing was prepared. Comparative Example 6 9 g of PVA (DP: 1700, DS: 87 to 90%) and 1 g of 16 201000550 of pentaerythritol were added to a mixer equipped with a stirrer, and added according to the total weight of PVA and pentaerythritol. 300 ppm of surfactant (BYK-337 'taken from BYK)' and a 70/30 (w/w) ratio of water to PGME as a solvent to give a solution viscosity of 60 cP. After stirring at room temperature and 500 rpm for 1 hour, a protective film composition for wafer cutting was prepared. Test Example 1: Measurement of Strip Rate Each sample of the examples and the comparative examples was coated on a 4 inch ruthenium oxide substrate by spin coating, and the rotation speed (rpm) was adjusted. The obtained film was dried at ll ° C for 15 minutes to have a thickness of Ι μη, thereby forming a protective film. The rate of removal of the protective film in water was measured using DRM. The unit of measurement is expressed in terms of the thickness of the film removed per second. The test results are shown in Table 1 below. ◎ : 1000 nm/s or more 〇: between 800 and less than 1000 nm/s △: between 500 and less than 800 nm/s x: less than 500 nm/s Test Example 2: Applicable Measurement of the properties Each sample of the examples and the comparative examples was applied by spin coating onto a 4 inch ruthenium oxide substrate, and the rotation speed (rpm) was adjusted so that the obtained film was at 11 (TC dried for 15 minutes) Ιμιη thickness' thus forms a protective film of 2010 201000. After that, the thickness of the film is measured at the center of the wafer and at a position spaced apart from the center of the wafer by 2 cm and 4 cm, and the standard deviation is determined, thereby evaluating the composition of the protective film. Applicability of the test. The test results are shown in the following table 1. ◎ : 1% or less 〇: more than 1% but not more than 2% △: more than 2% but not more than 4% X: more than 4% Test Example 3: Measurement of the pen hardness (Pencil Hardness) Each sample of the examples and the comparative examples was applied by spin coating on a 4 inch leaf size oxidized chopping substrate, and the obtained rotation speed (rpm) was used to make the obtained film After drying for 15 minutes at ll 〇 ° C, it has a thickness of Ι μηη, thus forming a protective film. Thereafter, according to HD D 0202 The hardness of the protective film on the pencil was measured. The test results are shown in the following Table 1. Test Example 4: Measurement of Adhesion Force Each sample of the examples and the comparative examples was applied by spin coating to an oxidized hard of 4 o'clock. On the substrate, and adjusting the rotation speed (rpm), the obtained film was dried at 11 CTC for 15 minutes to have a thickness of Ιμη, thereby forming a protective film. Thereafter, a cross-cut test (tape measurement test) was performed in accordance with JIS Κ 5600-5-6. (taping tast)) The test results are shown in Table 1. 18 201000550 ◎: number of detached lattices (0) 〇: number of separated lattices (between 1 and less than 5) △: separation Number of crystal lattices (between 5 and less than 10) X: Number of separated lattices (10 or more) Test Example 5: Measurement of thermal stability Each sample of the examples and the comparative examples was spin-coated It was coated on a 4 inch oxidized oxide substrate, and the obtained film was dried at 110 ° C for 15 minutes to have a thickness of Ιμηη, thereby forming a protective film. Thereafter, the protective film was placed at 250°. C hot air oven for 10 minutes, then check Whether it is washed away by water to confirm whether the water-insoluble pyrolyzed cross-linking material is heated. The test results are shown in the following Table 1. ◎: completely stripped state 〇: the presence of fine particles △: There are a large number of non-stripped portions x: unpeeled state Test Example 6: Measurement of storage stability Samples of the examples and comparative examples were stored at room temperature, and their viscosity and applicability were measured weekly to check properties. Whether it changes over time. The test results are shown in Table 1 below. ◎: Stable for 36 weeks or longer 19 201000550 〇: Stable for 18 weeks or longer △: Stable for 8 weeks or longer X: Stable for less than 8 weeks Table 1 Removal rate Applicability Pencil hardness Adhesion Thermal stability storage Stability Example 1 ◎ ◎ 7H ◎ ◎ 〇 Example 2 ◎ 〇 9H 〇 ◎ Example 3 ◎ 〇 9H 〇 〇 Example 4 ◎ ◎ 7H ◎ ◎ 〇 Example 5 ◎ ◎ 7H ◎ ◎ 〇 Example 6 ◎ 9 9H 〇 ◎ Example 7 ◎ ◎ 7H ◎ ◎ ◎ Example 8 ◎ ◎ 9H ◎ 〇 ◎ Example 9 ◎ ◎ 7H 〇 ◎ Example 1 ◎ ◎ 5H ◎ ◎ ◎ Comparative Example 1 Δ X 9H ◎ Δ 〇Comparative Example 2 〇 ◎ Η X Δ 〇 Comparative Example 3 Δ 〇Η X Δ 〇 Comparative Example 4 〇〇Η X Δ Δ Comparative Example 5 〇 ◎ Η X Δ 〇 Comparative Example 6 Δ 〇Η X Δ Δ It is intended to be illustrative, not limiting. Any changes or modifications to the spirit and scope of the present invention are intended to be included in the scope of the appended claims. 20 201000550 [Simple diagram description] None [Main component symbol description]

Claims (1)

201000550 七、申請專利範圍： l —種用於晶圓切割之保 、°蔓媒纟且成物，其包括： 至少一選自聚乙基„亞 之群組之樹脂；〜輕及聚乙㈣祕酮所組成 之=士選J *溶性樹脂及一酒精性單體所組成 之群組之成分；以及 Λ 一溶 處合物 ，係包含一水、或—水與一有 機溶劑之 2, 3 請專利範圍第1項所述之保護膜組成物，其中 至少-選自聚乙基噁唑啉及聚乙烯吡咯烷酮所 、:成之群組之樹脂，及該至少一選自一水溶性樹脂 酒精性單體所組成之群虹之成分，其使用之重 =比係為1 : 9〜7: 3 ’且使用該溶劑使該保護膜組 成物之總黏度係為l〇〜1〇〇eP。 =申請專利範圍帛1項所述之保護膜組成物，更包 士 一水溶性界面活性劑，依據該保護膜組成物之一 树脂成分之總重量，其用量係為1〇〜8〇 ppm。 如申請專利範圍第1項所述之保護膜組成物，其 Μ至少一選自聚乙基噁唑啉及聚乙烯吡咯烷酮所組成之 群組之樹脂係為聚乙基噁唑琳。 如申請專利範圍第1項所述之保護膜組成物，其中 »亥水溶性樹脂係選自聚乙烯醇、聚乙二醇（PEG)、 歎丙二醇（PPG)、纖維素及聚丙烯酸(PAA)所組成之 22 201000550 群組，且該酒精性單體係選自單乙二醇、二乙二 醇、三乙二醇、四乙二醇、丙二醇、環己二醇、環 己二曱醇、異戊四醇及三曱基丙醇所組成之群組。 6. 如申請專利範圍第1項所述之保護膜組成物，其中 該至少一選自一水溶性樹脂及一酒精性單體所組成 之群組之成分係為具87〜90%皂化度與500〜2000聚 合度之聚乙烯醇。 7. 如申請專利範圍第1項所述之保護膜組成物，其中 該至少一選自聚乙基噁唑啉及聚乙烯吡咯烷酮所組成之 群組之樹脂係為聚乙基噁唑啉，且該至少一選自一水 溶性樹脂及一酒精性單體所組成之群組之成分係 為具87〜90%皂化度與500〜2000聚合度之聚乙烯 醇。 8. 如申請專利範圍第3項所述之保護膜組成物，其中 該水溶性界面活性劑係選自聚醚修飾烧基石夕氧 烧、聚醚修飾聚院基>5夕氧炫*、具一經基之聚醚修飾 聚二曱基矽氧烷、具一羥基之聚醚-聚酯修飾聚烷 基石夕氧烧、一非離子聚丙烯水溶性界面活性劑、醇 烧氧基化物及一高分子含氣水溶性界面活性劑所組 成之群組之一或多個。 9. 如申請專利範圍第1項所述之保護膜組成物，其中 該溶劑係為該水與該有機溶劑之該混合物，且該有 機溶劑係選自異丙醇、丙二醇單曱基醚醋酸酯 (PGMEA)、丙二醇單曱基醚（PGME)、碳酸丁烯酯、 23 201000550 碳酸丙烯g旨、丙三醇碳酸酯及碳酸乙烯酯所組成之 群組之一或多個。 10. 如申請專利範圍第9項所述之保護膜組成物，其中 該有機溶劑係選自碳酸丁烯酯、碳酸丙烯酯、丙三 醇石反S文Sg及石反酸乙稀g旨所組成之群組之一或多個。 11. 一種半導體裝置，係利用如申請專利範圍第i至 Η項之任一項所述之保護膜組成物所製造。 24201000550 VII, the scope of application for patents: l - a type of wafer for cutting, 蔓 纟 纟 成 成 ° ° ° ° ° ° ° ° ° 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆a component consisting of a group of J* soluble resins and an alcoholic monomer; and a dissolved solution comprising water, or water and an organic solvent 2, 3 The protective film composition according to Item 1, wherein at least one selected from the group consisting of polyethyloxazoline and polyvinylpyrrolidone, a group of resins, and at least one selected from the group consisting of a water-soluble resin alcohol The component of the rainbow composed of the monomer is used in a weight ratio of 1:9 to 7:3' and the total viscosity of the protective film composition is l〇~1〇〇eP using the solvent. = Patent Application Scope 1 The protective film composition described above, further comprising a water-soluble surfactant, in an amount of from 1 〇 to 8 〇 ppm, based on the total weight of the resin component of one of the protective film compositions. The protective film composition according to claim 1, wherein at least one selected from the group consisting of The resin of the group consisting of ethyl oxazoline and polyvinylpyrrolidone is a polyethyl oxazoline. The protective film composition according to claim 1, wherein the water-soluble resin is selected from the group consisting of a group of 22 201000550 consisting of vinyl alcohol, polyethylene glycol (PEG), propylene glycol (PPG), cellulose and polyacrylic acid (PAA), and the alcoholic single system is selected from the group consisting of monoethylene glycol and diethylene glycol. a group consisting of alcohol, triethylene glycol, tetraethylene glycol, propylene glycol, cyclohexanediol, cyclohexanediol, pentaerythritol, and tridecylpropanol. The protective film composition, wherein the at least one component selected from the group consisting of a water-soluble resin and an alcoholic monomer is a polyvinyl alcohol having a degree of saponification of 87 to 90% and a polymerization degree of 500 to 2000. 7. The protective film composition according to claim 1, wherein the at least one resin selected from the group consisting of polyethyloxazoline and polyvinylpyrrolidone is polyethyloxazoline. And the at least one selected from the group consisting of a water-soluble resin and an alcoholic monomer A protective film composition having a degree of saponification of from 87 to 90% and a degree of polymerization of from 500 to 2,000. 8. The protective film composition of claim 3, wherein the water-soluble surfactant is selected from the group consisting of polyether modification Burning base stone oxy-sinter, polyether modified poly-based base>5 oxime oxy-*, polyether-modified polydidecyl fluorene with one-base, polyether-polyester modified polyalkyl sulphur One or more groups consisting of a non-ionic polypropylene water-soluble surfactant, an alcohol alkoxylate, and a polymer gas-containing water-soluble surfactant. 9. As claimed in claim 1 The protective film composition, wherein the solvent is the mixture of the water and the organic solvent, and the organic solvent is selected from the group consisting of isopropyl alcohol, propylene glycol monodecyl ether acetate (PGMEA), and propylene glycol monodecyl ether ( One or more of the group consisting of PGME), butylene carbonate, 23 201000550 propylene carbonate, glycerol carbonate, and ethylene carbonate. 10. The protective film composition according to claim 9, wherein the organic solvent is selected from the group consisting of butylene carbonate, propylene carbonate, glycerol anti-S text Sg, and sulphur acid One or more of the groups that make up. A semiconductor device manufactured by using the protective film composition according to any one of claims 1 to 3. twenty four
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