TW201630733A - 表面保護用膜片 - Google Patents
表面保護用膜片 Download PDFInfo
- Publication number
- TW201630733A TW201630733A TW104134628A TW104134628A TW201630733A TW 201630733 A TW201630733 A TW 201630733A TW 104134628 A TW104134628 A TW 104134628A TW 104134628 A TW104134628 A TW 104134628A TW 201630733 A TW201630733 A TW 201630733A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- curable resin
- meth
- wafer
- urethane
- Prior art date
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- 239000011347 resin Substances 0.000 claims abstract description 72
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 22
- 239000011231 conductive filler Substances 0.000 claims abstract description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 50
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
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Abstract
本發明提供可抑制膜片剝離後的晶圓彎曲,具有充分的帶電防止性能的表面保護用膜片。
本發明的表面保護用膜片,其係使用在電路形成在表面的半導體晶圓的背面研磨時的表面保護用膜片,其具有:基材,其係由包含無機導電性填充劑與硬化性樹脂(A)的硬化物的帶電防止塗層及支持薄膜所構成;及黏著劑層,在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上,基材的楊氏模量為100~2000MPa。
Description
本發明係關於將在表面形成電路的半導體晶圓的背面研磨時暫黏在該晶圓表面,用於保護電路圖案的表面保護用膜片。
近年,隨著電子機器的小型化、高積體化,進行其構成構件的半導體晶片的薄型化。因此,要求將原本為350μm左右的厚度的晶圓,薄化成50~100μm或其以下。
先前已在半導體晶圓表面形成電路圖案之後,將晶圓背面研磨。此時,在電路面黏貼被稱為表面保護用膜片的黏著膜片,進行電路面的保護及晶圓的固定,而進行背面研磨。研磨時,一般為去除產生的研磨屑及熱,將水噴霧在晶圓的研磨面。
先前的表面保護用膜片,係使用在基材上塗層黏著劑而成的黏著膜片。在專利文獻1,藉由使用應力緩和率高的表面保護用膜片,防止晶圓在背面研磨後的彎曲。
專利文獻1:日本特開2000-150432號公報
但是,使用專利文獻1的表面保護用膜片進行晶圓的背面研磨,則在將保護用膜片由晶圓表面剝離時,因剝離帶電而發生靜電,而有對形成在晶圓表面的電路造成損傷。近年,形成在晶圓表面的電路,由於線路微細化而高密度化,因剝離帶電所產生的靜電特別有問題。
防止如此的剝離帶電的靜電的手段,可考慮在表面保護用膜片形成帶電防止塗層。但是,現狀尚未能得到充分的帶電防止性能。
本發明係以提供可抑制膜片剝離後的晶圓彎曲,具有充分的帶電防止性能的表面保護用膜片為目標。
用於解決上述課題的本發明,包含以下的要點。
[1]一種表面保護用膜片,使用在電路形成在表面的半導體晶圓的背面研磨時的表面保護用膜片,其特徵在於:具有:基材,其係由包含無機導電性填充劑與硬化性樹脂(A)的硬化物的帶電防止塗層及支持薄膜所構成;及黏著劑層,在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上,基材的楊氏模量為100~2000MPa。
[2]如[1]所述的表面保護用膜片,其中帶電防止塗層,對硬化性樹脂(A)的硬化物100質量部,含有150~600質量部無機導電性填充劑。
[3]如[1]或[2]所述的表面保護用膜片,其中支持薄膜,包含硬化性樹脂(B)的硬化物。
[4]如[3]所述的表面保護用膜片,其中硬化性樹脂(B),係能量線硬化型含尿烷樹脂。
[5]一種表面保護用膜片的製造方法,其特徵在於具有:將包含硬化性樹脂(B)的調合物塗佈於工程膜片,預硬化,形成預硬化層的步驟;將包含無機導電性填充劑與硬化性樹脂(A)的調合物,塗佈於預硬化層,形成塗膜層的步驟;及使預硬化層與塗膜層硬化,形成基材的步驟。
根據本發明的表面保護用膜片,可抑制膜片剝離後的晶圓彎曲,且抑制因剝離帶電而產生靜電,防止晶圓電路因靜電而損傷。
1‧‧‧帶電防止塗層
2‧‧‧支持薄膜
3‧‧‧黏著劑層
5‧‧‧基材
10‧‧‧表面保護用模片
第1圖係將關於本發明的表面保護用膜片黏貼在半導體晶圓的狀態的剖面圖。
第2圖係表示半導體晶圓的電路形成面的平面圖。
以下,更具體說明關於本發明,及其最佳形態。如第1圖所示,關於本發明的表面保護用膜片10,係使用在進行電路12形成在表面的半導體晶圓11的背面研磨時,其具
有:基材5,其係由包含無機導電性填充劑與硬化性樹脂(A)之硬化物所構成的帶電防止塗層1及支持薄膜2所構成;及黏著劑層3,在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上,基材的楊氏模量為100~2000MPa。
[基材]
使用於本發明的表面保護用膜片的基材,係由帶電防止塗層與支持薄膜所構成。以下,依序說明帶電防止塗層、支持薄膜。
(帶電防止塗層)
帶電防止塗層,係披覆後述的支持薄膜的單面或兩面而形成。藉由設置帶電防止塗層,在將關於本發明的表面保護用膜片由被著體(例如半導體晶圓或半導體晶片等)剝離時可有效地使剝離帶電所產生的靜電擴散,提升帶電防止性能。帶電防止塗層,係由無機導電性填充劑與硬化性樹脂(A)的硬化物構成,可由使包含無機導電性填充劑與硬化性樹脂(A)之調合物硬化的方法而得。
無機導電性填充劑,並無特別限定,可舉例如Cu、Al、Ni、Sn、Zn等的金屬粉末等的金屬填充劑;或氧化鋅系、氧化鈦系、氧化錫系、氧化銦系、氧化銻系等的金屬氧化物填充劑。該等之中,相對較廉價,且有通用性,以氧化錫系的金屬氧化物填充劑為佳。氧化錫系的金屬氧化物填充劑,具體可使用銻摻雜氧化錫(ATO),磷摻雜氧化錫(PTO)等。
無機導電性填充劑的平均粒徑,並無特別限定,以0.01~1μm為佳,以0.02~0.5μm更佳。平均粒徑,係以粒度
分佈測定裝置(日機裝公司製的Microtrack UPA-150)測定之值。
帶電防止塗層,對硬化性樹脂(A)的硬化物100質量部,含有無機導電性填充劑150~600質量部為佳,以200~600質量部更佳,以220~600質量部特別佳。再者,通常硬化前的硬化性樹脂(A)及與無機導電性填充劑的調合量比,與硬化性樹脂(A)的硬化物及無機導電性填充劑的調合量比,大體上沒有差。因此,在本發明,將硬化前的硬化性樹脂(A)及無機導電性填充劑的調合量比,視為硬化性樹脂(A)的硬化物及無機導電性填充劑的調合量比。藉由使無機導電性填充劑在於帶電防止塗層的含量在上述範圍,可顯現優良的帶電防止性能,又,在加工半導體晶圓的步驟,可防止帶電防止塗層發生龜裂,結果,可更有效地抑制帶電防止性能的降低。
硬化性樹脂(A),並無特別限定,可使用能量線硬化型樹脂、熱硬化型樹脂等,而使用能量線硬化型樹脂為佳。
能量線硬化型樹脂,並無特別限定,可良好地使用例如,以能量線聚合性的尿烷(甲基)丙烯酸酯寡聚物、環氧(甲基)丙烯酸酯寡聚物等的寡聚物系能量線硬化型樹脂作為主劑的樹脂組成物。尿烷(甲基)丙烯酸酯寡聚物或環氧(甲基)丙烯酸酯寡聚物的重量平均分子量Mw(指以凝膠滲透層析之聚苯乙烯換算值。),通常為1000~70000左右,以1500~60000的範圍為佳。上述尿烷(甲基)丙烯酸酯寡聚物或環氧(甲基)丙烯酸酯寡聚物,可以一種單獨或組合二種以上使用。
使寡聚物系能量線硬化型樹脂在能量線硬化型樹
脂的含量變大,則有降低與後述的支持薄膜的密著性之情形。為提升與支持薄膜的密著性,亦可在硬化性樹脂(A)的成分中添加膠合劑成分。如此的膠合劑成分,可舉丙烯酸樹脂、聚酯樹脂、尿烷樹脂、聚醯胺樹脂等。
又,能量線硬化型樹脂,亦可係於側鏈具有能量線硬化性官能基的聚合物。使用如此的聚合物作為能量線硬化型樹脂,則可不降低架橋密度而提升與支持薄膜的密著性。如此的聚合物,可使用例如,主鏈為丙烯酸聚合物,於側鏈具有能量線硬化性雙鍵鍵結或環氧基作為官能基者。
藉由在能量線硬化型樹脂,混入光聚合起始劑,可減少藉由能量線照射的聚合硬化時間及照射量。光聚合起始劑,可舉安息香化合物、苯乙酮化合物、醯基氧化膦化合物、二茂鈦化合物、噻噸酮化合物、過氧化物等的光聚合起始劑;胺或醌等的光增感劑等,具體可舉1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-丙1-烷、安息香、安息香甲醚、安息香乙醚、安息香異丙醚等。
又,為提升無機導電性填充劑的樹脂中的分散性,亦可在硬化性樹脂(A)調合分散劑。又,亦可含有顏料或染料等的著色劑等的添加劑。
帶電防止塗層,可將含有無機導電性填充劑與硬化性樹脂(A)的調合物直接在後述的支持薄膜上製膜、硬化而形成。又,可將含有無機導電性填充劑與硬化性樹脂(A)的調合物以液體的狀態,以薄膜狀澆鑄在工程薄膜上,進一步在其上,將後述的含有硬化性樹脂(B)的調合物澆鑄,得到由帶電
防止塗層與支持薄膜所構成的基材。此時,進行硬化的程序,可在各個製膜之後,亦可在製膜基材之後,一口氣進行。
帶電防止塗層的厚度,以0.2~5μm,以0.5~5μm為佳,以1~4μm更佳。藉由使帶電防止塗層的厚度在上述範圍,有可維持較高的帶電防止性能的傾向。
又,帶電防止塗層的表面電阻率,以1×1012Ω/□以下為佳,以1×1011Ω/□以下更佳,以1×1010Ω/□以下特別佳。如帶電防止塗層的表面電阻率超過1×1012Ω/□,則在將本發明的表面保護用膜片由被著體剝離時,有難以穩定地抑制產生靜電之情形。藉由使帶電防止塗層的表面電阻率在上述範圍,可提升表面保護用膜片的帶電防止性能。帶電防止塗層的表面電阻率,係將帶電防止塗層裁切成100mm×100mm而得的樣品,在23℃、平均濕度50%RH的條件下調濕24小時之後,將其表面的阻抗值,遵照JIS K6911;1995測定。
(支持薄膜)
使用於本發明的表面保護用膜片的支持薄膜,只要是樹脂膜片,並無特別限定,可使用各種樹脂膜片。如此的樹脂膜片,可舉例如聚烯烴、聚氯乙烯、丙烯酸橡膠、尿烷等的樹脂薄膜。支持薄膜,可為該等的單層,亦可由層積體構成。又,亦可為施以架橋等的處理的薄膜。
如此的支持薄膜,可使用將熱可塑性樹脂藉由擠出成型膜片化者,亦可使用將硬化性樹脂(B)以既定手段薄膜化、硬化的硬化物所構成的薄膜。支持薄膜,使用硬化性樹脂(B)的硬化物所構成的薄膜,則基材的應力緩和率及楊氏模量
的控制變得容易的同時,可提升帶電防止塗層的密著性。
硬化性樹脂(B),並無特別限定,可與使用於帶電防止塗層的硬化性樹脂(A)同樣,使用能量線硬化型樹脂、熱硬化型樹脂等,而使用能量線硬化型樹脂為佳。能量線硬化型樹脂,並無特別限定,可使用例如能量線硬化型含尿烷樹脂。含有能量線硬化型含尿烷樹脂的硬化物的支持薄膜,由於應力緩和性優良,容易將基材的應力緩合率調整在後述的範圍而佳。
能量線硬化型含尿烷樹脂,可舉以尿烷(甲基)丙烯酸酯樹脂或尿烷聚合物、與能量線聚合性單體為主要成分的能量線硬化型樹脂。
尿烷(甲基)丙烯酸酯樹脂,係包含尿烷(甲基)丙烯酸酯寡聚物的調合物,按照必要亦可包含在分子內含有硫醇基的化合物、或N-亞硝胺系聚合禁止劑及/或N-氧基系聚合禁止劑。
尿烷(甲基)丙烯酸酯寡聚物,係具有(甲基)丙烯醯基,且具有尿烷鍵結的化合物。如此的尿烷(甲基)丙烯酸酯寡聚物,係多元醇化合物與多價異氰酸酯化合物反應而得的末端異氰酸酯尿烷預聚合物,與具有羥基的(甲基)丙烯酸酯反應而得。再者,在本說明書,(甲基)丙烯酸係以包含丙烯酸及甲基丙烯酸二者的意思使用。
多元醇化合物,只要是具有兩個羥基以上的化合物,並無特別限定,可使用習知者。具體可為例如,亞烷二醇、聚醚型多元醇、聚酯型多元醇、聚碳酸酯型多元醇的任一,藉
由使用聚醚型多元醇,可得更佳的效果。又,只要是多元醇,並無特別限定,可為2官能的二醇、3官能的三醇、再者亦可為4官能以上的多元醇,由取得的容易性、通用性、反應性等的觀點,使用二醇特別佳。該等之中,可良好地使用聚醚型二醇。
聚醚型多元醇的代表例之聚醚型二醇,一般係以HO-(-R-O-)n-H表示。在此,R係2價的碳化氫基、以亞烷基為佳,以碳數1~6的亞烷基更佳,以碳數2或3的亞烷基特別佳。又,碳數1~6的亞烷基之中,以乙烯、丙烯或四亞甲基更佳,以乙烯或丙烯特別佳。因此特別佳的聚醚型二醇,可舉聚乙二醇、聚丙二醇、聚四亞甲基二醇,再者特別佳的聚醚型二醇,可舉聚乙二醇、聚丙二醇。n係R的反覆數,以10~250左右為佳,以25~205左右更好,以40~185左右特別佳。n小於10,則尿烷(甲基)丙烯酸酯寡聚物的尿烷鍵結濃度變高,而支持薄膜的彈性躍昇,而使本發明的基材的楊氏模量變得過高。n大於250,則起因於聚醚鏈的相互作用變強,有使楊氏模量超過後述範圍的上限之虞。
藉由聚醚型二醇與多價異氰酸酯化合物的反應,生成導入醚鍵結部(-(-R-O-)n-)的末端異氰酸酯尿烷預聚合物。藉由使用如此的聚醚型二醇,尿烷(甲基)丙烯酸酯寡聚物,含有由聚醚型二醇衍生的構成單位。
聚酯型多元醇,可藉由多元醇化合物與多元酸成分聚縮合而得。多元醇化合物,可舉乙二醇、二甘醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊
二醇、戊二醇、3-甲基-1,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、己二醇、辛二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、1,4-環己烷二甲醇、雙酚A的乙二醇或丙二醇加成物等的習知的各種二醇類等。用於製造聚酯型多元醇的多元酸成分,可使用一般已知作為聚酯的多元酸成分的各種習知者。具體可舉例如己二酸、馬來酸、琥珀酸、草酸、富馬酸、丙二酸、戊二酸、庚二酸、壬二酸、癸二酸、辛二酸等的二元酸;芳香族多元酸;對應該等的酸酐;其衍生物及二聚物酸;加氫二聚物酸等。再者為對塗膜賦予適度的硬度,使用芳香族多元酸為佳。該芳香族多元酸,可舉例如無水鄰苯二甲酸、間苯二甲酸、對苯二甲酸、2,6-二羧酸等的二元酸;或偏苯三酸、均苯四甲酸等的多元酸及對應該等的酸酐或其衍生物。再者該酯化反應,亦可按照需要使用各種習知的觸媒。觸媒,可舉例如二丁基氧化錫、辛酸亞錫等的錫化合物或鈦酸四丁酯、鈦酸四丙酯等的烷氧基鈦。
聚碳酸酯型多元醇,並無特別限定,可使用習知者。具體可舉例如,上述乙二醇類與亞烷基碳酸酯的反應物等。
多元醇化合物的分子量,以500~10000左右為佳,以800~8000左右更佳。分子量較500低,則尿烷(甲基)丙烯酸酯寡聚物的尿烷鍵結濃度變高,使本發明的基材的楊氏模量變得過高。分子量過高,則起因於聚醚鏈的相互作用變強,有使楊氏模量超過後述範圍的上限之虞。
又,多元醇化合物的分子量,係多元醇官能基數×56.11×1000/羥基價[mgKOH/g],由多元醇化合物的羥基價計
算出。
多價異氰酸酯化合物,可舉四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯等的脂肪族系聚異氰酸酯類;異佛爾酮二異氰酸酯、降冰片烷二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、二環己基甲烷-2,4'-二異氰酸酯、ω,ω’-二異氰酸酯二甲基環己烷等的脂環族系二異氰酸酯類;4,4'-二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、二異氰酸聯甲苯胺、四亞甲基二甲苯二異氰酸酯、萘-1,5-二異氰酸酯等的芳香族系二異氰酸酯類等。該等之中,使用異佛爾酮二異氰酸酯或六亞甲基二異氰酸酯、二甲苯二異氰酸酯,可維持尿烷(甲基)丙烯酸酯寡聚物的低黏度,使操作性良好而佳。
對如上所述的多元醇化合物,與多價異氰酸酯化合物反應而得的末端異氰酸酯尿烷預聚合物,使具有羥基的(甲基)丙烯酸酯反應可得尿烷(甲基)丙烯酸酯寡聚物。
具有羥基的(甲基)丙烯酸酯,只要是在1分子中具有羥基及(甲基)丙烯醯基的化合物,並無特別限定,可使用習知者。具體可舉例如2-羥基乙基(甲基)丙烯酸酯、2-羥基(甲基)丙基丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、4-羥環己基(甲基)丙烯酸酯、5-羥基環辛基(甲基)丙烯酸酯、2-羥基-3-苯基氧丙基(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、丙二醇單(甲基)丙烯酸酯等的羥基烷基(甲基)丙烯酸酯、N-羥甲基(甲基)丙烯醯胺等的含有羥基的(甲基)丙烯醯胺、使(甲基)丙烯酸與雙酚A的二縮水甘油基反應而得的
反應物等。
使具有末端異氰酸酯尿烷預聚合物及羥基的(甲基)丙烯酸酯反應的條件,係將具有有末端異氰酸酯尿烷預聚合物與羥基丙烯酸酯,按照需要在溶劑、觸媒的存在下,以60~100℃左右反應1~4小時左右即可。
所得尿烷(甲基)丙烯酸酯寡聚物,係在分子內具有光聚合性的雙鍵鍵結,可藉由能量線的照射而聚合硬化,形成皮膜的性質。上述尿烷(甲基)丙烯酸酯寡聚物,可以一種單獨或組合二種以上使用。尿烷(甲基)丙烯酸酯寡聚物,可為分子中僅具有1個(甲基)丙烯醯基的單官能尿烷是丙烯酸酯寡聚物,亦可為分子中具有2個以上的(甲基)丙烯醯基的多官能尿烷是丙烯酸酯寡聚物,以多官能尿烷(甲基)丙烯酸酯寡聚物為佳。尿烷(甲基)丙烯酸酯寡聚物為多官能尿烷(甲基)丙烯酸酯寡聚物,則如後所述,有藉由調整尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量,可容易控制所得基材的楊氏模量優點。具有多官能尿烷(甲基)丙烯酸酯寡聚物的(甲基)丙烯醯基的數量,以2~3個為佳,以2個(尿烷(甲基)丙烯酸酯寡聚物為二官能尿烷(甲基)丙烯酸酯寡聚物)更佳。
尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量(指以凝膠滲透層析之聚苯乙烯換算值,以下相同。),並無特別限定,尿烷(甲基)丙烯酸酯寡聚物為多官能尿烷(甲基)丙烯酸酯寡聚物時,重量平均分子量以1500~10000左右為佳,以4000~9000左右更佳。藉由使重量平均分子量為1500以上,可抑制尿烷(甲基)丙烯酸酯寡聚物的聚合物的架橋密度的上
升,而容易將基材的楊氏模量調整在不超過後述的範圍的上限的程度。又,藉由使之在10000以下,抑制尿烷(甲基)丙烯酸酯寡聚物在聚合物的架橋密度的降低,可容易調整基材的楊氏模量不低過後述的範圍的下限。又,可使尿烷(甲基)丙烯酸酯寡聚物的黏度較低,提升製膜用塗佈液的操作性。
使用如上所述的尿烷(甲基)丙烯酸酯時,由於難以成膜支持薄膜的情形較多,通常係以能量線聚合性單體稀釋成膜之後,將此硬化得到支持薄膜。能量線聚合性單體,係於分子內具有能量線聚合性的雙鍵鍵結,特別是在本發明,使用異冰片基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、苯基羥基丙基(甲基)丙烯酸酯等的具有體積較大的基的(甲基)丙烯酸酯系化合物為佳。
上述能量線聚合性單體,對尿烷(甲基)丙烯酸酯寡聚物100質量部,以5~900質量部為佳,以10~500質量部更佳,以30~200質量部的比例使用特別佳。藉由使能量線聚合性單體的調合量在如此的範圍,在尿烷(甲基)丙烯酸酯寡聚物與能量線聚合性單體的共聚物,來自尿烷(甲基)丙烯酸酯寡聚物的(甲基)丙烯醯基的部分的間隔成為適當的程度,可容易將基材的楊氏模量控制在後述的範圍。
能量線硬化型含尿烷樹脂,可使用以尿烷聚合物與能量線聚合性單體為主要成分的能量線硬化型樹脂,將該能量線硬化型樹脂硬化而得之支持薄膜亦可。
尿烷聚合物,係與尿烷(甲基)丙烯酸酯寡聚物不同,係在分子中沒有(甲基)丙烯醯基等的聚合性官能基的尿烷系聚合
體,例如可使上述的多元醇化合物與多價異氰酸酯化合物反應而得。
能量線聚合性單體,可使用與上述相同將尿烷(甲基)丙烯酸酯樹脂稀釋者之外,亦可使用N,N-二甲基胺基乙基丙烯酸酯、N,N-二甲基胺基丙基甲基丙烯醯胺、丙烯醯基嗎啉、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、醯亞胺丙烯酸酯、N-乙烯基咯烷酮等的含氮單體。
上述能量線聚合性單體,對尿烷聚合物100質量部,以5~900質量部為佳,以10~500質量部更佳,以30~200質量部的比例使用特別佳。
將支持薄膜,由上述能量線硬化型樹脂形成時,藉由在該樹脂混入光聚合起始劑,可減少藉由能量線照射的聚合硬化時間及照射量。光聚合起始劑,可混入與混入硬化性樹脂(A)之相同者。
光聚合起始劑的使用量,對能量線硬化型樹脂100質量部,以0.05~15質量部為佳,以0.1~10質量部更佳,以0.5~5質量部特別佳。
又,亦可在上述硬化性樹脂(B)中,含有碳酸鈣、二氧化矽、雲母等的無機填充劑;鐵、鉛等的金屬填充劑;顏料或染料等的著色劑等的添加劑。
支持薄膜的製膜方法,可藉由將包含硬化性樹脂(B)的調合物以液狀的狀態薄膜狀澆鑄在工程薄膜上之後,將此以既定的手段薄膜化,藉由去除工程薄膜而製造支持薄膜。根據如此的製法,樹脂在製膜時所受到應力較小,不容易發生
因經時或加熱的尺寸變化。又,由於容易去除固體雜質,故所製膜的薄膜較少形成魚眼,藉此可提升膜厚的均勻性,而厚度精度,通常在2%以內。
支持薄膜的厚度,以40~300μm為佳,以60~250μm更佳,以80~200μm特別佳。
再者,支持薄膜的形成帶電防止塗層的面或設置黏著劑層的面,為提升與該等層的密著性,亦可施以電暈處理,或施以底層處理等設置其他的層。
藉由如上所述的原材料及方法所製膜的支持薄膜,顯示優良的應力緩和性。例如,藉由採用該應力緩和性優良的支持薄膜等,使用於本發明的基材顯示優良的應力緩和性。具體而言,在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上,以65%以上為佳,以75~90%更佳。藉由使基材的應力緩和率在上述範圍,使用該基材的本發明的表面保護用膜片,可迅速的消除在黏貼於被著體時所產生的殘留應力,在研磨半導體晶圓的背面的步驟(加工半導體晶圓的步驟),將半導體晶圓研磨的極薄時,亦可抑制半導體晶圓的彎曲。若基材的應力緩和率未滿60%以下,則半導體晶圓會因在加工半導體晶圓的步驟所產生的應力而發生彎曲。
又,基材的楊氏模量為100~2000MPa,以125~1500MPa為佳,以125~1000MPa更佳,以125~700MPa特別佳。在表面保護用膜片設置帶電防止塗層,則有在晶圓的背面研磨步驟,帶電防止塗層發生龜裂(斷裂)之情形。因出現該龜裂,切斷帶電防止塗層的面方向的導電性,而有降低將剝
離帶電擴散的效果。根據本發明的表面保護用膜片,藉由使基材的楊氏模量在上述範圍,對表面保護用膜片的拉伸賦予適當的耐性,防止帶電防止塗層的龜裂,可抑制帶電防止性能的下降。基材的楊氏模量未滿100MPa,則帶電防止塗層會發生龜裂,而降低帶電防止性能。又,基材的楊氏模量超過2000MPa,則降低基材的應力緩和率,難以得到具有所期望範圍的應力緩和率的基材,降低防止晶圓彎曲的效果。
[黏著劑層]
本發明的表面保護用膜片,於帶電防止塗層上或支持薄膜上形成黏著劑層。
黏著劑層,只要對晶圓有適當的再剝離性,其種類並無特定,可由先前已知的各種黏著劑形成。如此的黏著劑,並無任何限定,可使用例如,橡膠系、丙烯酸系、矽酮系、尿烷系、聚乙烯基醚等的黏著劑。又,亦可使用藉由能量線的照射而硬化成為再剝離性的能量線硬化型黏著劑、或加熱發泡型、水膨潤型的黏著劑。
能量線硬化(紫外線硬化、電子線硬化)型黏著劑,特別是使用紫外線硬化型黏著劑為佳。如此的能量線硬化型黏著劑的具體例,可舉例如日本特開昭60-196956號公報及日本特開昭60-223139號公報所記載。又,作為水膨潤型黏著劑,可良好地使用例如日本特公平5-77284號公報、日本特公平6-101455號公報等所記載者。
黏著劑層的厚度,並無特別限定,以5~300μm為佳,以10~200μm的範圍更佳。
又,在黏著劑層,亦可在其使用前層積用於保護黏著劑層的剝離膜片。剝離膜片,並無特別限定,可使用對剝離膜片用基材以剝離劑處理者。剝離膜片用基材,可舉例如,聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚丙烯、聚乙烯等的樹脂所構成的薄膜或該等的發泡薄膜、玻璃紙、塗層紙、層壓紙等的紙。剝離劑,可舉矽酮系、氟系、含有長鏈烷基的碳酸酯等的剝離劑。
於基材表面設置黏著劑層的方法,可將以既定膜厚塗佈形成在剝離膜片上的黏著劑層轉印在基材表面,亦可將黏著劑層直接塗佈形成在基板表面。
[表面保護用膜片]
本發明的表面保護用膜片,係在由上述帶電防止塗層與支持薄膜所構成的基材的一面形成黏著劑層而得。黏著劑層,可設於帶電防止塗層上或支持薄膜上。再者,在於第1圖,係於支持薄膜2上形成黏著劑層3。
表面保護用膜片的製造方法,並無特別限定,例如可藉由具有:將包含硬化性樹脂(B)的調合物塗佈於工程膜片上,使之硬化,得到支持薄膜的步驟;將包含無機導電性填充劑與硬化性樹脂(A)的調合物塗佈於支持薄膜上,形成塗膜層的步驟;使塗膜層硬化,形成基材的步驟的製造方法製造。之後,藉由在基材的一面形成黏著劑層,可得關於本發明的表面保護用膜片。藉由上述製造方法所得的表面保護用膜片的基材,以將包含硬化性樹脂(B)的調合物塗佈於工程膜片,預備硬化,形成預備硬化層的步驟;將包含無機導電性填充劑與硬
化性樹脂(A)的調合物塗佈於預備硬化層上,形成塗膜層的步驟;將預備硬化層與塗膜層硬化的步驟形成為佳。即,在預備硬化狀態的支持薄膜的表面上,形成成為帶電防止塗層的塗佈層,一口氣將支持薄膜與帶電防止塗層完全硬化,故帶電防止塗層與支持薄膜的密著性優良,又,可提升帶電防止性能。
再者,在上述表面保護用膜片的製造方法,亦可在預備硬化的階段使硬化性樹脂(B)完全硬化。以如此的製造方法,亦可提升帶電防止塗層與支持薄膜的密著性。
又,表面保護用膜片的製造方法,可舉將帶電防止塗層與支持薄膜分別製膜,層積得到基材,在基材上形成黏著劑層的方法。
[半導體晶圓的加工方法]
本發明的表面保護用膜片,可如下所述用於半導體晶圓的加工。
(晶圓背面研磨方法)
在晶圓的背面研磨,如第1圖所示,在電路12形成在表面的半導體晶圓11的電路面上黏貼表面保護用膜片10邊保護電路面,將晶圓的背面以研磨機20研磨,作成既定厚度的晶圓。
半導體晶圓可謂矽晶圓,又,亦可為砷化鎵等的化合物半導體晶圓。對晶圓表面的電路形成,可藉由包含蝕刻法、舉離法等的先前通用的方法的各式各樣的方法進行。在半導體晶圓的電路形成步驟,形成既定的電路。如第2圖所示,電路12係在晶圓11的內周部13表面形成格子狀,在外周端
的數mm的範圍殘存著不存在電路的剩餘部分14。如此的晶圓的研磨前的厚度,並無特別限定,通常為500~1000μm程度。
背面研磨時,如第1圖所示,於電路面黏貼用於保護晶圓表面的電路12的本發明的表面保護用膜片10。表面保護用膜片對晶圓表面的黏貼,係使用膠帶貼合機等的通用的手法進行。又,表面保護用膜片10,可預先切成與半導體晶圓11大致同形狀,亦可將膜片黏貼在晶圓之後,將多餘的膜片沿著晶圓外周切斷,去除。
晶圓的背面研磨,係將電路全面以表面保護用膜片10黏貼的狀態,使用研磨機20及用於固定晶圓的吸盤(無圖示)等的習知的手法進行。背面研磨步驟之後,亦可進行去除因研磨所生成的破碎層的處理。背面研磨後的半導體晶圓的厚度,並無特別限定,以10~500μm為佳,以25~300μm程度特別佳。
背面研磨步驟之後,將表面保護用膜片10由電路面剝離。根據本發明的表面保護用膜片,晶圓的背面研磨時,可將晶圓確實地保持,又,可防止切削水滲入電路面。又,背面研磨結束之後,將膜片10由晶圓表面剝離時,可有效地將剝離帶電所產生的靜電擴散。
接著,經由晶圓的切割、晶片的構裝、樹脂封裝等的步驟,得到半導體裝置。
(先切割法)
再者,又,本發明的表面保護用膜片,可良好的使用於所謂以先切割法的具有高凸塊的晶圓的晶片化。具體而言,係由
表面形成有具有凸塊的電路的半導體晶圓表面,形成較該晶圓厚度淺的切入深度的溝,在該電路形成面,黏貼表面保護用膜片,之後,藉由將半導體晶圓的背面研磨,使晶圓厚度變薄的同時,最終進行分割成各個晶片。
之後,以既定的方法進行晶片拾取。又,亦可在拾取晶片之前,將整列成晶圓形狀的狀態的晶片,轉印在其他的黏著膜片,之後,進行晶片拾取。根據本發明的表面保護用膜片,將保護用膜片由晶片剝離時,可有效地使剝離帶電所產生的靜電擴散。
實施例
以下,以實施例說明本發明,惟本發明不應限定於該等實施例。再者,在以下的實施例及比較例,各種物性係如下進行評估。
<基材的楊氏模量>
基材的楊氏模量,係使用萬能拉伸試驗機(ORIENTEC公司製的萬能拉力機RTA-T-2M),遵照JIS K7161:1994,在於23℃、濕度50%的環境下,以拉伸速度200mm/分測定。
<基材的應力緩和率>
將使用於實施例或比較例的基材,切出寬度15mm、長度100mm得到試驗片。將該試驗片,使用ORIENTEC公司製的萬能拉力機RTA-100,在室溫(23℃),拉伸速度200mm/分拉伸。以擴張10%的狀態停止拉伸,以此時的應力A,及停止擴張1分鐘後的應力B,基於應力緩和率=(A-B)/A×100(%)之式,計算應力緩和率。
<研磨後的晶圓彎曲>
將實施例或比較例所製作的表面保護用膜片,使用膠帶貼合機(LINTEC公司製Adwill RAD-3500),黏貼於矽晶圓(200mmψ,厚度750μm)。之後,使用DISCO公司製DFG-840,將矽晶圓研磨成厚度150μm。研磨之後,不去除表面保護用膜片,使表面保護用膜片朝上,將晶圓載置在遵照JIS B 7513;1992的平面度1級的精密檢查用固定盤上。
測定係以固定盤作為零點,測定17處測定點。彎曲量,係最大值與最小值之差。
<剝離帶電>
在晶圓電路面,黏貼實施例或比較例的表面保護用膜片,得到晶圓與表面保護用膜片的層積體。將層積體,由製作層積體後,放置在平均溫度約23℃,平均濕度65%RH的環境下30天。放置後,首先,將層積體裁切成10×10cm的四角形。接著,將表面保護用膜片以500mm/分由晶圓剝離。此時,將在表面保護用膜片所帶電的帶電電位,以集電式電位測定儀(春日電機公司製KSD-6110),由50mm的距離,以23℃,濕度65%RH的環境下測定(測定下限值0.1kV)。
<帶電防止塗層的龜裂>
以與評估研磨後的晶圓彎曲的相同方法研磨晶圓之後,將表面保護用膜片由晶圓剝離,將帶電防止塗層面以數位顯微鏡觀察,確認帶電防止塗層有無龜裂。
(實施例1)
將包含以分子量2000的聚酯型多元醇與異佛爾酮二異氰
酸酯合成的尿烷寡聚物作為骨架,於其末端加成2-羥基乙基丙烯酸酯而得之二官能尿烷丙烯酸酯寡聚物(重量平均分子量8000)50質量部,丙烯酸系單體(能量線聚合性單體)之異冰片基丙烯酸酯25質量部及2-羥基-3-苯氧基丙基丙烯酸酯25質量部的混合物,及光聚合起始劑之DAROCURE1173(產品名,BASF公司製)1質量部的調合物,塗佈展延在剝離薄膜上,以紫外線使之硬化得到厚度100μm的支持薄膜。
對環氧基丙烯酸酯系樹脂100質量部(質量平均分子量2000),調合平均粒徑0.1μm的銻摻雜氧化錫(ATO)230質量部、光聚合起始劑(BASF公司製的IRGACURE184)2質量部得到調合物。將該調合物塗佈在支持薄膜的一面,藉由照射紫外線設置厚度2μm的帶電防止塗層。另一方面,在支持薄膜的設置帶電防止塗層之面的相反面,塗佈20μm厚的紫外線硬化型黏著劑,設置黏著劑層製作表面保護用膜片。將各評估結果示於第1表。
(實施例2)
在支持薄膜的製造,使尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量為3000以外,以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。
(實施例3)
在支持薄膜的製造,使尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量為6000,ATO的添加量為400質量部,帶電防止塗層的厚度為0.25μm以外,以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。
(實施例4)
使ATO的添加量為150質量部,帶電防止塗層的厚度作為4.8μm以外,以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。
(比較例1)
沒有設置帶電防止塗層以外,以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。
(比較例2)
在支持薄膜的製造,使尿烷丙烯酸酯寡聚物的重量平均分子量為12000以外,以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。
(比較例3)
在支持薄膜的製造,使尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量作為900之外和實施例1一樣製作表面保護用膜片了。將各評估結果示於第1表。
1‧‧‧帶電防止塗層
2‧‧‧支持薄膜
3‧‧‧黏著劑層
5‧‧‧基材
10‧‧‧表面保護用模片
Claims (5)
- 一種表面保護用膜片,使用在電路形成在表面的半導體晶圓的背面研磨時的表面保護用膜片,其特徵在於:具有:基材,其係由包含無機導電性填充劑與硬化性樹脂(A)的硬化物的帶電防止塗層及支持薄膜所構成;及黏著劑層,在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上,基材的楊氏模量為100~2000MPa。
- 如申請專利範圍第1項所述的表面保護用膜片,其中帶電防止塗層,對硬化性樹脂(A)的硬化物100質量部,含有150~600質量部無機導電性填充劑。
- 如申請專利範圍第1或2項所述的表面保護用膜片,其中支持薄膜,包含硬化性樹脂(B)的硬化物。
- 如申請專利範圍第3項所述的表面保護用膜片,其中硬化性樹脂(B),係能量線硬化型含尿烷樹脂。
- 一種表面保護用膜片的製造方法,其特徵在於具有:將包含硬化性樹脂(B)的調合物塗佈於工程膜片,預硬化,形成預硬化層的步驟;將包含無機導電性填充劑與硬化性樹脂(A)的調合物,塗佈於預硬化層,形成塗膜層的步驟;及使預硬化層與塗膜層硬化,形成基材的步驟。
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JPH0616524B2 (ja) | 1984-03-12 | 1994-03-02 | 日東電工株式会社 | 半導体ウエハ固定用接着薄板 |
JPS60223139A (ja) | 1984-04-18 | 1985-11-07 | Nitto Electric Ind Co Ltd | 半導体ウエハ固定用接着薄板 |
JPS63153814A (ja) | 1986-07-09 | 1988-06-27 | F S K Kk | ウエハ貼着用粘着シ−ト |
JPH06101455B2 (ja) | 1987-05-27 | 1994-12-12 | リンテック株式会社 | ウエハ研摩用保護シ−トおよびこのシ−トを用いたウエハ面の研摩方法 |
JP3499957B2 (ja) * | 1995-03-10 | 2004-02-23 | リンテック株式会社 | 帯電防止粘着シート |
JP3383227B2 (ja) | 1998-11-06 | 2003-03-04 | リンテック株式会社 | 半導体ウエハの裏面研削方法 |
JP4307825B2 (ja) * | 2002-08-28 | 2009-08-05 | リンテック株式会社 | 半導体ウエハの保護構造、半導体ウエハの保護方法、これらに用いる積層保護シートおよび半導体ウエハの加工方法 |
JP4704225B2 (ja) * | 2006-01-30 | 2011-06-15 | 富士フイルム株式会社 | アルバム作成装置、アルバム作成方法、およびアルバム作成プログラム |
JP2007296751A (ja) * | 2006-04-28 | 2007-11-15 | Mitsubishi Plastics Ind Ltd | 樹脂積層体 |
JP2010177542A (ja) * | 2009-01-30 | 2010-08-12 | Lintec Corp | 帯電防止性粘着シート |
JP5788165B2 (ja) * | 2010-11-02 | 2015-09-30 | 三菱樹脂株式会社 | 難燃性樹脂フィルム及びそのフィルムの製造方法 |
-
2015
- 2015-10-21 JP JP2016555257A patent/JP6559150B2/ja active Active
- 2015-10-21 CN CN201580055315.9A patent/CN107078042B/zh active Active
- 2015-10-21 WO PCT/JP2015/079724 patent/WO2016063916A1/ja active Application Filing
- 2015-10-21 US US15/520,121 patent/US10224230B2/en active Active
- 2015-10-21 KR KR1020177007415A patent/KR102407903B1/ko active IP Right Grant
- 2015-10-22 TW TW104134628A patent/TWI688476B/zh active
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TWI688476B (zh) | 2020-03-21 |
US20170323820A1 (en) | 2017-11-09 |
KR102407903B1 (ko) | 2022-06-10 |
CN107078042A (zh) | 2017-08-18 |
KR20170075712A (ko) | 2017-07-03 |
US10224230B2 (en) | 2019-03-05 |
CN107078042B (zh) | 2021-05-04 |
JPWO2016063916A1 (ja) | 2017-08-03 |
JP6559150B2 (ja) | 2019-08-14 |
WO2016063916A1 (ja) | 2016-04-28 |
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