TW202311317A - 切割保護層用之樹脂組成物及半導體晶圓的加工方法 - Google Patents
切割保護層用之樹脂組成物及半導體晶圓的加工方法 Download PDFInfo
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- TW202311317A TW202311317A TW111125284A TW111125284A TW202311317A TW 202311317 A TW202311317 A TW 202311317A TW 111125284 A TW111125284 A TW 111125284A TW 111125284 A TW111125284 A TW 111125284A TW 202311317 A TW202311317 A TW 202311317A
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- FQQOMIXCGMRXEH-UHFFFAOYSA-N hydroxy-methyl-phenyl-propylsilane Chemical group CCC[Si](C)(O)C1=CC=CC=C1 FQQOMIXCGMRXEH-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
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- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VLKDZHUARIPFFA-UHFFFAOYSA-N tert-butyl-hydroxy-methyl-phenylsilane Chemical group CC(C)(C)[Si](C)(O)C1=CC=CC=C1 VLKDZHUARIPFFA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical group O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 1
- QQUBYBOFPPCWDM-UHFFFAOYSA-N trihydroxy-(4-trihydroxysilylphenyl)silane Chemical group O[Si](O)(O)C1=CC=C([Si](O)(O)O)C=C1 QQUBYBOFPPCWDM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
本揭示的一方面係有關一種切割保護層用之樹脂組成物,其含有:具有羧基之丙烯酸樹脂及有機溶劑。
Description
本揭示係有關一種切割保護層用之樹脂組成物及半導體晶圓的加工方法。
半導體裝置通常經由以下步驟製造。首先,將半導體晶圓貼附於切割用黏著片,並在其狀態下將半導體晶圓單片化為半導體晶片(切割步驟)。其後,實施拾取步驟、壓接步驟、晶粒接合步驟等,製作半導體裝置。
在切割步驟中,有可能因半導體晶圓的切削而產生之微細切削物附著於半導體晶圓的電路形成面上,從而在隨後的步驟中產生連接不良。因此,研究了在半導體晶圓上設置保護層之後進行切割步驟,並在切割後去除保護層。例如,作為用於形成保護層之材料,在專利文獻1中揭示了將環狀結構的糖作為基本骨架之非水溶性多糖類,在專利文獻2中揭示了包含來自於酸酐的單體結構單元之共聚物。
[專利文獻1]日本特開2014-172932號公報
[專利文獻2]日本特開2018-129365號公報
半導體晶圓的保護層要求在切割時不從半導體晶圓剝離或不溶解於切割時所使用之冷卻水中。另一方面,由於保護層在切割後被去除,因此要求溶解於用於去除保護層之鹼水溶液中。
本揭示的目的為提供一種能夠形成切割半導體晶圓時的密接性優異並且切割後的去除性優異之保護層之切割保護層用之樹脂組成物、及使用該樹脂組成物之半導體晶圓的加工方法。
本揭示的一方面係有關以下切割保護層用之樹脂組成物及半導體晶圓的加工方法。
[1]一種切割保護層用之樹脂組成物,其含有:具有羧基之丙烯酸樹脂及有機溶劑。
[2]如上述[1]所述之樹脂組成物,其中
前述丙烯酸樹脂具有來自於(甲基)丙烯酸之結構單元。
[3]如上述[2]所述之樹脂組成物,其中
前述丙烯酸樹脂還具有來自於(甲基)丙烯酸烷基酯之結構單元。
[4]如上述[1]至[3]之任一項所述之樹脂組成物,其中
前述丙烯酸樹脂的重量平均分子量為10000~100000。
[5]如上述[1]至[4]之任一項所述之樹脂組成物,其中
前述有機溶劑包含選自由二醇醚系溶劑及脂肪族羧酸酯系溶劑組成的組中的至少一種。
[6]一種半導體晶圓的加工方法,其具備:使用上述[1]至[5]之任一項所述之切割保護層用之樹脂組成物,在半導體晶圓上形成保護層之步驟;切割形成有前述保護層之半導體晶圓之步驟;及藉由鹼水溶液從前述切割之半導體晶圓去除前述保護層之步驟。
[7]如上述[6]所述之半導體晶圓的加工方法,其中
前述保護層的厚度為0.3~3.0μm。
[發明效果]
依據本揭示,能夠提供一種能夠形成切割半導體晶圓時的密接性優異並且切割後的去除性優異之保護層之切割保護層用之樹脂組成物、及使用該樹脂組成物之半導體晶圓的加工方法。
以下,對本揭示進行詳細說明。但是,本發明並不限定於以下實施形態。在本說明書中,所謂「(甲基)丙烯酸」係指「丙烯酸」及與其對應之「甲基丙烯酸」的至少一者,關於(甲基)丙烯酸酯等其他類似表達亦相同。又,所謂「A或B」包含A和B中的任一個即可,亦可以包含兩者。此外,所謂「固體成分」係指除組成物中所包含之水、溶劑等揮發物質以外的不揮發成分,表示乾燥該組成物時不揮發而殘留之成分,還包含在25℃左右的室溫下呈液狀、麥芽糖狀及蠟狀者。關於組成物中的各成分的含量,組成物中存在複數種相當於各成分之物質之情況下,只要沒有特別說明,則係指存在於組成物中之該複數種物質的合計量。以下所例示之材料等只要沒有特別說明,則可以單獨使用,亦可以將2種以上組合使用。
在本說明書中,使用「~」所表示之數值範圍是表示將「~」前後記載之數值分別作為最小值和最大值而包含在內之範圍。在本說明書中階段性記載之數值範圍內,某一階段的數值範圍的上限值或下限值亦可以替換成其他階段的數值範圍的上限值或下限值。在本說明書中所記載之數值範圍內,其數值範圍的上限值或下限值可以替換為實施例所示之值。
[切割保護層用之樹脂組成物]
本實施形態之樹脂組成物含有:具有羧基之丙烯酸樹脂(以下,有時簡稱為「丙烯酸樹脂」。)及有機溶劑。
(丙烯酸樹脂)
從使其在鹼水溶液中的溶解性變得良好之觀點考慮,本實施形態之丙烯酸樹脂具有羧基。羧基能夠藉由對具有羧基之單體進行自由基聚合而導入。
作為具有羧基之單體,例如可以舉出(甲基)丙烯酸、α-溴(甲基)丙烯酸、α-氯(甲基)丙烯酸、β-氟(甲基)丙烯酸、β-苯乙烯(甲基)丙烯酸、富馬酸、桂皮酸、α-氰基桂皮酸、衣康酸、巴豆酸、及丙炔酸。從提高對鹼水溶液的溶解性之觀點考慮,丙烯酸樹脂具有來自於(甲基)丙烯酸之結構單元為較佳。
從提高切割時的耐水性與在鹼水溶液中的溶解性的平衡之觀點考慮,來自於(甲基)丙烯酸之結構單元的含量以來自於構成丙烯酸樹脂之單體之結構單元的總質量為基準,可以為5~25質量%、8~20質量%、或10~15質量%。
從提高切割時的耐水性之觀點考慮,丙烯酸樹脂還可以具有來自於(甲基)丙烯酸烷基酯之結構單元。丙烯酸樹脂例如能夠藉由使(甲基)丙烯酸與(甲基)丙烯酸烷基酯進行自由基聚合來製造。
作為(甲基)丙烯酸烷基酯,例如可以舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、及(甲基)丙烯酸二十烷基酯。
從進一步提高切割時的耐水性之觀點考慮,來自於(甲基)丙烯酸烷基酯之結構單元的含量以來自於構成丙烯酸樹脂之單體之結構單元的總質量為基準,可以為40質量%以上、50質量%以上、或55質量%以上。從進一步提高在鹼水溶液中的溶解性之觀點考慮,來自於(甲基)丙烯酸烷基酯之結構單元的含量以來自於構成丙烯酸樹脂之單體之結構單元的總質量為基準,可以為90質量%以下、88質量%以下、或85質量%以下。
從進一步提高切割時的耐水性之觀點考慮,丙烯酸樹脂還可以具有來自於苯乙烯或苯乙烯衍生物之結構單元。作為苯乙烯衍生物,例如可舉出乙烯基甲苯、α-甲基苯乙烯、對甲基苯乙烯及對乙基苯乙烯。
從進一步提高在鹼水溶液中的溶解性之觀點考慮,丙烯酸樹脂可以具有羥基。作為具有羥基之單體,例如可以舉出(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸2-羥丁酯、及甘油單(甲基)丙烯酸酯。
丙烯酸樹脂可以具有上述以外的結構單元。作為提供這種結構單元之單體,例如可以舉出(甲基)丙烯酸苄酯或其衍生物、丙烯腈、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸環氧丙酯、2,2,2-三氟乙基(甲基)丙烯酸酯、及2,2,3,3-四氟丙基(甲基)丙烯酸酯。
從進一步提高在鹼水溶液中的溶解性之觀點考慮,丙烯酸樹脂的酸值可以為50mgKOH/g以上、60mgKOH/g以上、或70mgKOH/g以上,從提高切割時的耐水性之觀點考慮,丙烯酸樹脂的酸值可以為150mgKOH/g以下、140mgKOH/g以下、或130mgKOH/g以下。
丙烯酸樹脂的重量平均分子量(Mw)可以為10000~100000、15000~90000、20000~80000、30000~70000、或40000~60000。當丙烯酸樹脂的Mw為10000以上時,容易提高成膜性,當為100000以下時,容易藉由鹼水溶液而去除。在此,Mw為藉由凝膠滲透色譜(GPC)法測定,並藉由標準聚苯乙烯的檢量線進行換算而得之值。
本實施形態之樹脂組成物中的丙烯酸樹脂的含量例如可以為5~30質量%、8~25質量%、或10~20質量%。
(有機溶劑)
作為本實施形態之有機溶劑,能夠使用能夠溶解丙烯酸樹脂並在形成保護層時容易去除之溶劑。從提高樹脂組成物的成膜性之觀點考慮,有機溶劑包含選自由二醇醚系溶劑及脂肪族羧酸酯系溶劑組成的組中的至少一種為較佳。
作為二醇醚系溶劑,例如可以舉出乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、丙二醇二甲醚、丙二醇二***、丙二醇二丙醚、及丙二醇二丁醚。
作為脂肪族羧酸酯系溶劑,例如可以舉出乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸異丙酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸異丙酯、丙酸正丁酯、及丙酸異丁酯。
(調平劑)
本實施形態之樹脂組成物還可以含有調平劑。藉由將調平劑摻合到樹脂組成物中,能夠防止條痕(縮孔、不均勻等)而提高對半導體晶圓的塗佈性。
作為調平劑,例如可以舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、及聚氧乙烯辛基苯酚醚。作為調平劑的市售品,例如可以舉出Megaface F171、F173、R-08(DIC Corporation製、商品名稱)、Fluorad FC430、FC431(3M Japan Limited製、商品名稱)、有機矽氧烷聚合物KP341、KBM303、KBM403、KBM803(Shin-Etsu Chemical Co., Ltd.製、商品名稱)。
使用調平劑時的摻合量相對於丙烯酸樹脂100質量份,可以為0.01~5質量份、0.03~3質量份、或0.05~2質量份。
(偶合劑)
本實施形態之樹脂組成物還可以含有偶合劑。藉由將偶合劑摻合到樹脂組成物中,切割時容易抑制保護層的剝離。作為偶合劑,例如可以舉出有機矽烷化合物及鋁螯合物化合物。
作為有機矽烷化合物,例如可以舉出乙烯基三乙氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、脲丙基三乙氧基矽烷、甲基苯基矽烷二醇、乙基苯基矽烷二醇、正丙基苯基矽烷二醇、異丙基苯基矽烷二醇、正丁基苯基矽烷二醇、異丁基苯基矽烷二醇、第三丁基苯基矽烷二醇、二苯基矽烷二醇、乙基甲基苯基矽烷醇、正丙基甲基苯基矽烷醇、異丙基甲基苯基矽烷醇、正丁基甲基苯基矽烷醇、異丁基甲基苯基矽烷醇、第三丁基甲基苯基矽烷醇、乙基正丙基苯基矽烷醇、乙基異丙基苯基矽烷醇、正丁基乙基苯基矽烷醇、異丁基乙基苯基矽烷醇、第三丁基乙基苯基矽烷醇、甲基二苯基矽烷醇、乙基二苯基矽烷醇、正丙酯二苯基矽烷醇、異丙酯二苯基矽烷醇、正丁酯二苯基矽烷醇、異丁酯二苯基矽烷醇、第三丁基二苯基矽烷醇、苯基矽烷三醇、1,4-雙(三羥基甲矽烷基)苯、1,4-雙(甲基二羥基甲矽烷基)苯、1,4-雙(乙基二羥基甲矽烷基)苯、1,4-雙(丙基二羥基甲矽烷基)苯、1,4-雙(丁基二羥基甲矽烷基)苯、1,4-雙(二甲基羥基甲矽烷基)苯、1,4-雙(二乙基羥基甲矽烷基)苯、1,4-雙(二丙基羥基甲矽烷基)苯、及1,4-雙(二丁基羥基甲矽烷基)苯。
使用偶合劑時的摻合量相對於丙烯酸樹脂100質量份,可以為0.1~10質量份、0.3~8質量份、或0.5~5質量份。
使用本實施形態之樹脂組成物形成於半導體晶圓上之保護層在切割時對半導體晶圓的密接性優異,切割後能夠藉由鹼水溶液容易地去除。
[半導體晶圓的加工方法]
本實施形態之半導體晶圓的加工方法具備:使用上述切割保護層用之樹脂組成物,在半導體晶圓上形成保護層之步驟;切割形成有保護層之半導體晶圓之步驟;及藉由鹼水溶液從切割之半導體晶圓去除保護層之步驟。
在半導體晶圓上形成保護層之方法並無特別限定,可以將上述樹脂組成物藉由旋塗等方法塗佈於半導體晶圓上,並藉由乾燥形成保護層,亦可以將成為保護層之樹脂層形成於脫模膜上之後,在半導體晶圓上貼合樹脂層後剝離脫模膜而形成。
本實施形態之保護層由於密接性及耐水性優異,因此能夠在切割時保護半導體晶圓。從提高切割時的保護性之觀點考慮,保護層的厚度可以為0.3μm以上、0.5μm以上、或0.8μm以上,從縮短剝離時間之觀點考慮,保護層的厚度可以為3.0μm以下、2.0μm以下、或1.5μm以下。亦即,保護層的厚度可以為0.3~3.0μm、0.5~2.0μm、或0.8~1.5μm。
作為用於去除保護層之鹼水溶液,例如可以舉出氨水溶液及四甲基氫氧化銨(TMAH)水溶液。鹼水溶液的濃度在氨水溶液的情況下可以為0.01~5質量%、0.1~3.0質量%以下、或0.5~2.0質量%,在TMAH水溶液的情況下可以為0.1~10質量%、0.5~5質量%以下、或1.0~5.0質量%。保護層的去除例如可以在5~30℃下進行5~300秒。
去除保護層之後的經加工之半導體晶圓能夠用於與其他半導體晶圓或半導體晶片的連接。在本實施形態之半導體晶圓的加工方法中,由於能夠防止因半導體晶圓的切削而產生之微細的切削物附著於半導體晶圓上,因此能夠降低在隨後的步驟中連接不良的產生。
[實施例]
以下,依據實施例具體地說明本揭示,但是本發明並不限定於以下實施例。
[丙烯酸樹脂的合成]
(合成例1)
向具備攪拌器、冷卻器、氣體導入管、滴液漏斗、及溫度計之燒瓶中添加丙二醇單甲醚乙酸酯80質量份及乳酸乙酯80質量份,導入氮氣並且80℃下進行了攪拌。接著,將作為單體之甲基丙烯酸26質量份、甲基丙烯酸甲酯110質量份、及丙烯酸丁酯64質量份與作為聚合起始劑之2,2’-偶氮雙(異丁腈)3質量份與丙二醇單甲醚乙酸酯44質量份及乳酸乙酯44質量份的混合物經3小時滴加到燒瓶內之後,在80℃下攪拌4小時,進一步在100℃下攪拌了2小時。其後,冷卻至室溫而獲得了丙烯酸樹脂(P-1)的溶液(固體成分45質量%)。P-1的Mw為43000。
丙烯酸樹脂的Mw為藉由GPC來測定並使用標準聚苯乙烯的檢量線換算而得之值。作為測定裝置使用TOSOH CORPORATION製的「HLC-8320GPC」、作為管柱使用Showa Denko Materials co., Ltd.製的「Gelpack GL-A150-S/GL-A160-S」、作為溶析液使用四氫呋喃,在流量1mL/分鐘、柱溫40℃的條件下測定了Mw。校準曲線使用標準聚苯乙烯的5個樣品組(TOSOH CORPORATION製的PStQuick MP-H、PStQuick B)按照JIS K 7252-2(2016)用通用校準曲線的3次方來近似。
(合成例2)
除了將單體變更為丙烯酸26質量份、苯乙烯60質量份、及丙烯酸丁酯114質量份以外,以與合成例1相同的方式獲得了丙烯酸樹脂(P-2)的溶液。P-2的Mw為46000。
(合成例3)
除了將單體變更為甲基丙烯酸22質量份、甲基丙烯酸2-羥乙酯34質量份、甲基丙烯酸甲酯42質量份、及丙烯酸丁酯102質量份以外,以與合成例1相同的方式獲得了丙烯酸樹脂(P-3)的溶液。P-3的Mw為44000。
[切割保護層用之樹脂組成物的製備及保護層的形成]
(實施例1)
將丙烯酸樹脂(P-1)的溶液10質量份與乳酸乙酯20質量份混合,並使用孔徑0.5μm的過濾器過濾,從而製備了樹脂組成物。
使用旋塗機(MIKASA CO., LTD、商品名稱「Opticoat MS-A200」)在500rpm/5秒、接著2000rpm/30秒的條件下,在25℃下將樹脂組成物旋塗於6英吋的矽晶圓(厚度0.625mm)上,在設定為100℃之熱板上加熱2分鐘,在矽晶圓上形成了厚度1.1μm的保護層。
(實施例2)
除了將丙烯酸樹脂(P-1)的溶液變更為丙烯酸樹脂(P-2)的溶液以外,以與實施例1相同的方式製備樹脂組成物,並使用該樹脂組成物在矽晶圓上形成了厚度1.2μm的保護層。
(實施例3)
除了將丙烯酸樹脂(P-1)的溶液變更為丙烯酸樹脂(P-3)的溶液以外,以與實施例1相同的方式製備樹脂組成物,並使用該樹脂組成物在矽晶圓上形成了厚度1.2μm的保護層。
(比較例1)
將苯乙烯馬來酸酐共聚物(Polyscope公司、商品名稱「XIRAN-1000」、Mw:5000)20質量份與4質量%的氨水溶液80質量份混合,並使用孔徑0.5μm的過濾器進行過濾,從而製備了樹脂組成物。嘗試使用該樹脂組成物在矽晶圓上形成保護層,但由於產生縮孔及不均勻,無法形成評價用之保護層。
(比較例2)
將苯乙烯馬來酸酐共聚物(Polyscope公司、商品名稱「XIRAN-3000」、Mw:10000)13質量份與4質量%的氨水溶液87質量份混合,並使用孔徑0.5μm的過濾器進行過濾,從而製備了樹脂組成物。除了使用該樹脂組成物以外,以與實施例1相同的方式在矽晶圓上形成了厚度0.9μm的保護層。
[評價]
對形成有保護層之矽晶圓,進行了以下評價。將結果示於表1中。
(外觀)
以目視確認保護層的外觀,將在保護層上沒有縮孔及不均勻之情況判斷為OK,將在保護層上有縮孔或不均勻之情況判斷為NG。
(切割性)
使用切割機(DISCO Corporation、商品名稱「DAD3350」)及切割刀片(DISCO Corporation、商品名稱「ZH05-SD4500-N1-70-DD」),在主軸轉速每分鐘30000rpm、進給速度50mm/s的條件下,以晶片尺寸成為縱5mm、橫5mm之方式切割了形成有保護層之矽晶圓。切割後,使用顯微鏡觀察了保護層的縱橫切割線交點附近。將無保護膜的溶解及剝離之情況判斷為OK,將有保護層的溶解或剝離之情況判斷為NG。
(溶解性)
作為鹼水溶液,準備了1.0質量%的氨水溶液及2.38質量%的TMAH水溶液。將藉由切割而獲得之帶保護層之晶片在23℃下浸漬於鹼水溶液,並測定了保護膜的溶解時間。將保護層的溶解時間為60秒以內之情況判斷為OK,將保護層的溶解時間超過60秒之情況判斷為NG。
[表1]
實施例 | 比較例 | |||||
1 | 2 | 3 | 1 | 2 | ||
保護層的厚度(μm) | 1.1 | 1.2 | 1.2 | - | 0.9 | |
保護層的外觀 | OK | OK | OK | NG | OK | |
切割性 | OK | OK | OK | - | NG(剝離) | |
溶解性 | 氨水溶液 | OK | OK | OK | - | OK |
TMAH水溶液 | OK | OK | OK | - | OK |
Claims (7)
- 一種切割保護層用之樹脂組成物,其含有:具有羧基之丙烯酸樹脂及有機溶劑。
- 如請求項1所述之樹脂組成物,其中 前述丙烯酸樹脂具有來自於(甲基)丙烯酸之結構單元。
- 如請求項2所述之樹脂組成物,其中 前述丙烯酸樹脂還具有來自於(甲基)丙烯酸烷基酯之結構單元。
- 如請求項1所述之樹脂組成物,其中 前述丙烯酸樹脂的重量平均分子量為10000~100000。
- 如請求項1所述之樹脂組成物,其中 前述有機溶劑包含選自由二醇醚系溶劑及脂肪族羧酸酯系溶劑組成的組中的至少一種。
- 一種半導體晶圓的加工方法,其具備: 使用請求項1至請求項5之任一項所述之切割保護層用之樹脂組成物在半導體晶圓上形成保護層之步驟; 切割形成有前述保護層之半導體晶圓之步驟;及 藉由鹼水溶液從前述切割後之半導體晶圓去除前述保護層之步驟。
- 如請求項6所述之半導體晶圓的加工方法,其中 前述保護層的厚度為0.3~3.0μm。
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