TWI512846B - Water-based protective film formation liquid - Google Patents
Water-based protective film formation liquid Download PDFInfo
- Publication number
- TWI512846B TWI512846B TW100122329A TW100122329A TWI512846B TW I512846 B TWI512846 B TW I512846B TW 100122329 A TW100122329 A TW 100122329A TW 100122329 A TW100122329 A TW 100122329A TW I512846 B TWI512846 B TW I512846B
- Authority
- TW
- Taiwan
- Prior art keywords
- protective film
- water
- wafer
- liquid
- concave portion
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims description 132
- 239000007788 liquid Substances 0.000 title claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 53
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000005871 repellent Substances 0.000 claims description 71
- 238000004140 cleaning Methods 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 36
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 125000000962 organic group Chemical group 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 115
- 125000001309 chloro group Chemical group Cl* 0.000 description 47
- 239000000243 solution Substances 0.000 description 28
- -1 decyl compound Chemical class 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
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- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
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Description
本發明係關於一種目的在於在半導體元件製造等時,提高尤其微細且縱橫比較高之經電路圖案化之元件之製造良率的晶圓之洗淨技術。尤其係關於一種用以防止表面上具有凹凸圖案之晶圓之凹凸圖案倒塌的保護膜形成用藥液。
對於網路或數位家電用之半導體元件,要求進一步之高性能、高功能化或低消耗電力化。因此,進行電路圖案之微細化,隨之亦使引起製造良率下降之顆粒尺寸微小化。其結果,較多使用目的在於去除經微小化之顆粒等污染物質之洗淨步驟,其結果使洗淨步驟竟然佔據半導體製造步驟整體之3~4成。
另一方面,先前進行之利用氨之混合洗淨劑進行之洗淨時,隨著電路圖案之微細化,其鹼性對晶圓之損害成為問題。因此,發展替換成損害更少之例如稀氫氟酸系洗淨劑。
藉此,雖然改善洗淨對晶圓之損害之問題,但隨著半導體元件之微細化使得圖案之縱橫比提高所引起之問題趨於明顯化。即,於洗淨或沖洗後,氣液界面通過圖案時會引起圖案倒塌之現象,且良率大幅下降成為較大之問題。
該圖案倒塌係於自洗淨液或沖洗液中提起晶圓時產生。認為其原因在於:於圖案之縱橫比較高之部分與較低之部分之間產生殘液高度的差異,藉此作用於圖案之毛細管力
產生差異。
由此,若減輕毛細管力,則可期待殘液高度不同所引起之毛細管力之差異下降,並消除圖案倒塌。毛細管力之大小係根據以下所示之式求出之P的絕對值,若根據該式減小γ或cosθ,則期待可降低毛細管力。
P=2×γ×cosθ/S(式中,γ為保持於凹部之液體之表面張力,θ為凹部表面與保持於凹部之液體所成之接觸角,S為凹部之寬度)。
於專利文獻1中揭示有於氣液界面通過之前,將洗淨液由水置換成2-丙醇之技術作為減小γ而抑制圖案倒塌之方法。
又,於專利文獻2中揭示有以抗蝕劑圖案作為對象之技術作為減小cosθ而抑制圖案倒塌之方法。該方法係將接觸角設為90°附近,藉此使cosθ接近於0而將毛細管力降低至極限為止,從而抑制圖案倒塌之方法。
又,於專利文獻3中揭示一種如下之洗淨方法:對由含有矽之膜形成凹凸形狀圖案之晶圓表面藉由氧化等進行表面改質,使用水溶性界面活性劑或矽烷偶合劑而於該表面上形成撥水性保護膜,降低毛細管力,藉此防止圖案之倒塌。
專利文獻1:日本專利特開2008-198958號公報
專利文獻2:日本專利特開平5-299336號公報
專利文獻3:日本專利第4403202號
於專利文獻3中揭示有六甲基二矽氮烷、四甲基矽烷基二乙胺作為形成撥水性保護膜之矽烷偶合劑。本發明之課題在於,於將表面上形成有凹凸圖案之晶圓中該凹凸圖案之至少凹部表面含有矽元素之晶圓洗淨時,提供一種含有矽化合物之保護膜形成用藥液,作為形成對於防止圖案之倒塌可產生良好之撥水性能之保護膜的試劑。
本發明者等人為解決上述課題而進行努力研究,發現為防止圖案之倒塌(以下於本文中記作「圖案倒塌」),若使用含有通式[1]所示之具有與1個氫原子之鍵結的矽化合物(以下於本文中記作「二烷基矽烷基化合物」)之保護膜形成用藥液,作為降低作用於毛細管力之撥水性保護膜之形成劑(以下記作「撥水性保護膜形成劑」或「保護膜形成劑」)[化1]R 2 (H)SiX [1]
藥液[式中,R分別相互獨立,為選自含有碳數為1~18之烴基之一價有機基、及含有碳數為1~8之氟烷基鏈之一價有機基中的至少1種基,X為選自鹵素原子、或與矽元素鍵結之元素為氮之一價有機基中的至少1種基],則所形成之保護膜與例如使用六甲基二矽氮烷等之類的三烷基矽烷基化
合物所形成之情形相比,可產生良好之撥水性(參照實施例3vs比較例1、實施例6vs比較例2)。又,本發明者等人發現可藉由使用含有具有特定之結構之矽化合物與作為觸媒之酸或鹼的藥液,而形成撥水性優異之保護膜,雖然已經申請(日本專利特願2011-091952號),但獲得如下見解:若使用本發明之二烷基矽烷基化合物,則無需使作為觸媒之酸或鹼共存,而獲得具有良好之撥水性之保護膜(參照實施例1~6)。
即,本發明提供以下之[發明1]~[發明5]中記載之發明。
一種撥水性保護膜形成用藥液,其係於將表面上具有凹凸圖案且該凹凸圖案之至少一部分含有矽元素之晶圓洗淨時,用以於該凹凸圖案之至少凹部表面上形成保護膜者,且含有下述通式[1]所示之二烷基矽烷基化合物,不含有酸及鹼。
[化2]R 2 (H)SiX [1]
[式中,R分別相互獨立,為選自含有碳數為1~18之烴基之一價有機基、及含有碳數為1~8之氟烷基鏈之一價有機基中的至少1種基,X為選自鹵素原子、或與矽元素鍵結之元素為氮之一價有機基中的至少1種基]。
如發明1之撥水性保護膜形成用藥液,其中上述通式[1]中之X為鹵素原子。
如發明1之撥水性保護膜形成用藥液,其中上述通式[1]中之X為與矽元素鍵結之元素為氮之一價有機基。
如發明1之撥水性保護膜形成用藥液,其中通式[1]所示之二烷基矽烷基化合物係通式[2]所示。
[化3]R 2 (H)Si-NH-Si(H)R 2 [2]
[式中,R與通式[1]相同]。
一種晶圓之洗淨方法,其係將表面上形成有凹凸圖案之晶圓中該凹凸圖案之至少凹部表面含有矽元素之晶圓洗淨者,且包括:利用水系洗淨液洗淨上述晶圓表面之水系洗淨液洗淨步驟;於上述晶圓之至少凹部保持撥水性保護膜形成用藥液,且於該凹部表面上形成撥水性保護膜之撥水性保護膜形成步驟;去除晶圓表面之液體之液體去除步驟;及自上述凹部表面去除撥水性保護膜之撥水性保護膜去除步驟;且於撥水性保護膜形成步驟中使用如發明1至發明3中任一項之撥水性保護膜形成用藥液。
於專利文獻3中,藉由將形成於凹凸圖案表面上之羥基
與三烷基矽烷基進行鍵結,而形成撥水性保護膜。可認為由於烴基具有疏水性,故而使用最大量矽元素鍵結有烴基之三烷基矽烷基化合物形成撥水性保護膜較為有效,意外地發現若使用矽上鍵結之烴基數為2個之二烷基矽烷基化合物形成撥水性保護膜,則與三烷基矽烷基化合物之情形相比,撥水性提昇。
藉由使用本發明之晶圓圖案保護膜形成用藥液,而將表面上形成有含有矽元素之凹凸圖案的晶圓洗淨時,有助於形成顯示出良好之撥水性之保護膜。
以下對本發明進行進而詳細之說明。
首先,對本發明中提供之用以防止圖案倒塌之撥水性保護膜形成用藥液(以下記作「撥水性保護膜形成用藥液」、「保護膜形成用藥液」,或僅記作「藥液」)之特徵即通式[1]所示之二烷基矽烷基化合物進行說明。
於通式[1]所示之二烷基矽烷基化合物中,R分別相互獨立為選自含有碳數為1~18之烴基之一價有機基、及含有碳數為1~8之氟烷基鏈之一價有機基中的至少1種基,X表示選自鹵素原子、或與矽元素鍵結之元素為氮之一價有機基中的至少1種基。於通式[1]中,於作為X之矽元素上鍵結之元素為氮的一價有機基中,不僅可含有氫、碳、氮、氧,亦可含有矽、硫、鹵素元素等。
其中,作為X所示之鹵素原子,可列舉:氟原子、氯原子、碘原子、溴原子。例如於X為氯原子之情形時,可列舉:(CH3
)2
(H)Si-Cl、C2
H5
(CH3
)(H)Si-Cl、(C2
H5
)2
(H)Si-Cl、C3
H7
(CH3
)(H)Si-Cl、(C3
H7
)2
(H)Si-Cl、C4
H9
(CH3
)(H)Si-Cl、(C4
H9
)2
(H)Si-Cl、C5
H11
(CH3
)(H)Si-Cl、(C5
H11
)2
(H)Si-Cl、C6
H13
(CH3
)(H)Si-Cl、(C6
H13
)2
(H)Si-Cl、C7
H15
(CH3
)(H)Si-Cl、(C7
H15
)2
(H)Si-Cl、C8
H17
(CH3
)(H)Si-Cl、(C8
H17
)2
(H)Si-Cl、C9
H19
(CH3
)(H)Si-Cl、(C9
H19
)2
(H)Si-Cl、C10
H21
(CH3
)(H)Si-Cl、(C10
H21
)2
(H)Si-Cl、C11
H23
(CH3
)(H)Si-Cl、(C11
H23
)2
(H)Si-Cl、C12
H25
(CH3
)(H)Si-Cl、(C12
H25
)2
(H)Si-Cl、C13
H27
(CH3
)(H)Si-Cl、(C13
H27
)2
(H)Si-Cl、C14
H29
(CH3
)(H)Si-Cl、(C14
H29
)2
(H)Si-Cl、C15
H31
(CH3
)(H)Si-Cl、(C15
H31
)2
(H)Si-Cl、C16
H33
(CH3
)(H)Si-Cl、(C16
H33
)2
(H)Si-Cl、C17
H35
(CH3
)(H)Si-Cl、(C17
H35
)2
(H)Si-Cl、C18
H37
(CH3
)(H)Si-Cl、(C18
H37
)2
(H)Si-Cl、CF3
C2
H4
(CH3
)(H)Si-Cl、C2
F5
C2
H4
(CH3
)(H)Si-Cl、C3
F7
C2
H4
(CH3
)(H)Si-Cl、C4
F9
C2
H4
(CH3
)(H)Si-Cl、C5
F11
C2
H4
(CH3
)(H)Si-Cl、C6
F13
C2
H4
(CH3
)(H)Si-Cl、C7
F15
C2
H4
(CH3
)(H)Si-Cl、C8
F17
C2
H4
(CH3
)(H)Si-Cl等。
又,作為通式[1]之X所示之與矽元素鍵結之元素為氮的一價有機基,可列舉:異氰酸酯基、胺基、二烷基胺基、疊氮基、乙醯胺基、咪唑基、-NH-Si(H)R2
基(R與通式[1]相同)等。例如於X為-NH-Si(H)R2
基之情形時,可列舉:(CH3
)2
(H)Si-NH-Si(H)(CH3
)2
、C2
H5
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H5
、(C2
H5
)2
(H)Si-NH-Si(H)(C2
H5
)2
、C3
H7
(CH3
)(H)Si-
NH-Si(H)(CH3
)C3
H7
、(C3
H7
)2
(H)Si-NH-Si(H)(C3
H7
)2
、C4
H9
(CH3
)(H)Si-NH-Si(H)(CH3
)C4
H9
、(C4
H9
)2
(H)Si-NH-Si(H)(C4
H9
)2
、C5
H11
(CH3
)(H)Si-NH-Si(H)(CH3
)C5
H11
、(C5
H11
)2
(H)Si-NH-Si(H)(C5
H11
)2
、C6
H13
(CH3
)(H)Si-NH-Si(H)(CH3
)C6
H13
、(C6
H13
)2
(H)Si-NH-Si(H)(C6
H13
)2
、C7
H15
(CH3
)(H)Si-NH-Si(H)(CH3
)C7
H15
、(C7
H15
)2
(H)Si-NH-Si(H)(C7
H15
)2
、C8
H17
(CH3
)(H)Si-NH-Si(H)(CH3
)C8
H17
、(C8
H17
)2
(H)Si-NH-Si(H)(C8
H17
)2
、C9
H19
(CH3
)(H)Si-NH-Si(H)(CH3
)C9
H19
、(C9
H19
)2
(H)Si-NH-Si(H)(C9
H19
)2
、C10
H21
(CH3
)(H)Si-NH-Si(H)(CH3
)C10
H21
、(C10
H21
)2
(H)Si-NH-Si(H)(C10
H21
)2
、C11
H23
(CH3
)(H)Si-NH-Si(H)(CH3
)C11
H23
、(C11
H23
)2
(H)Si-NH-Si(H)(C11
H23
)2
、C12
H25
(CH3
)(H)Si-NH-Si(H)(CH3
)C12
H25
、(C12
H25
)2
(H)Si-NH-Si(H)(C12
H25
)2
、C13
H27
(CH3
)(H)Si-NH-Si(H)(CH3
)C13
H27
、(C13
H27
)2
(H)Si-NH-Si(H)(C13
H27
)2
、C14
H29
(CH3
)(H)Si-NH-Si(H)(CH3
)C14
H29
、(C14
H29
)2
(H)Si-NH-Si(H)(C14
H29
)2
、C15
H31
(CH3
)(H)Si-NH-Si(H)(CH3
)C15
H31
、(C15
H31
)2
(H)Si-NH-Si(H)(C15
H31
)2
、C16
H33
(CH3
)(H)Si-NH-Si(H)(CH3
)C16
H33
、(C16
H33
)2
(H)Si-NH-Si(H)(C16
H33
)2
、C17
H35
(CH3
)(H)Si-NH-Si(H)(CH3
)C17
H35
、(C17
H35
)2
(H)Si-NH-Si(H)(C17
H35
)2
、C18
H37
(CH3
)(H)Si-NH-Si(H)(CH3
)C18
H37
、(C18
H37
)2
(H)Si-NH-Si(H)(C18
H37
)2
、CF3
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
CF3
、C2
F5
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
C2
F5
、C3
F7
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
C3
F7
、C4
F9
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
C4
F9
、C5
F11
C2
H4
(CH3
)(H)Si-NH-Si(H)
(CH3
)C2
H4
C5
F11
、C6
F13
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
C6
F13
、C7
F15
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
C7
F15
、C8
F17
C2
H4
(CH3
)(H)Si-NH-Si(H)(CH3
)C2
H4
C8
F17
等。
通式[1]所示之二烷基矽烷基化合物中,若R之碳數為1~8,則由於可短時間內形成上述保護膜,故而較佳。
又,作為X所示之鹵素原子,較佳為氯原子。進而,X所示之與矽元素鍵結之元素為氮的一價有機基中,較佳為-NH-Si(H)R2
基。
進而,若考慮獲取之容易程度等,則作為上述通式[1]所示之矽化合物中尤其較佳之化合物,可列舉:二甲基氯矽烷、四甲基二矽氮烷。
繼而,對含有通式[1]所示之二烷基矽烷基化合物之撥水性保護膜形成用藥液進行說明。只要本發明之藥液中至少含有撥水性保護膜形成劑即可。
上述藥液可使用有機溶劑作為溶劑。只要該有機溶劑為溶解上述保護膜形成劑者即可,例如可較佳地使用烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、不具有羥基之多元醇之衍生物、含氮化合物溶劑等。
作為上述烴類之例,有甲苯、苯、二甲苯、己烷、庚烷、辛烷等,作為上述酯類之例,有乙酸乙酯、乙酸丙酯、乙酸丁酯、乙醯乙酸乙酯等,作為上述醚類之例,有二乙醚、二丙醚、二丁醚、四氫呋喃、二噁烷等,作為上
述酮類之例,有丙酮、乙醯丙酮、甲基乙基酮、甲基丙基酮、甲基丁基酮、環己酮等,作為上述含鹵素溶劑之例,有全氟辛烷、全氟壬烷、全氟環戊烷、全氟環己烷、六氟苯等全氟碳,1,1,1,3,3-五氟丁烷、八氟環戊烷、2,3-二氫十氟戊烷、Zeorora H(日本ZEON股份有限公司製造)等氫氟碳,甲基全氟異丁醚、甲基全氟丁醚、乙基全氟丁醚、乙基全氟異丁醚、Asahiklin AE-3000(旭硝子股份有限公司製造)、Novec HFE-7100、Novec HFE-7200、Novec7300、Novec7600(均為3M公司製造)等氫氟醚,四氯甲烷等氯碳,氯仿等氫氯碳,二氯二氟甲烷等氯氟碳,1,1-二氯-2,2,3,3,3-五氟丙烷、1,3-二氯-1,1,2,2,3-五氟丙烷、1-氯-3,3,3-三氟丙烯、1,2-二氯-3,3,3-三氟丙烯等氫氯氟碳,全氟醚、全氟聚醚等;作為上述亞碸系溶劑之例,有二甲基亞碸等;作為上述不具有羥基之多元醇衍生物之例,有二乙二醇單乙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、二乙二醇二甲醚、二乙二醇乙基甲基醚、二乙二醇二乙醚、二乙二醇單甲醚乙酸酯、二乙二醇二乙酸酯、三乙二醇二甲醚、三乙二醇二乙醚、二丙二醇二甲醚、乙二醇二乙酸酯、乙二醇二乙醚、乙二醇二甲醚等;作為含氮化合物溶劑之例,有甲醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、二乙胺、三乙胺、吡啶等。該等溶劑中,尤其可較佳使用Novec HFE-7100等氫氟醚、丙二醇單甲醚乙酸酯等不具有羥基之多元醇之衍生
物。
又,進而若上述有機溶劑使用不燃性者,則由於撥水性保護膜形成用藥液成為不燃性,或燃點提高,故而較佳。含鹵素溶劑由於不燃性者較多,可較佳使用不燃性含鹵素溶劑作為不燃性有機溶劑。
又,有機溶劑中亦可存在微量之水分。但是,若該水分大量含於溶劑中,則有時二烷基矽烷基化合物由於該水分而進行水解,反應性會下降。因此,較佳為降低溶劑中之水分量,該水分量較佳為100質量ppm以下,進而尤其較佳為50質量ppm以下。
又,本發明之撥水性保護膜形成用藥液無需含有酸或鹼作為觸媒,而可形成具有撥水性能之保護膜,但此處所謂「不含有酸及鹼」,具體而言,意指相對於該藥液總量,酸或鹼為100質量ppm以下。
進而,只要該二烷基矽烷基化合物以相對於上述藥液之總量100質量%為0.1~50質量%之方式加以混合則較佳,更佳為相對於該藥液之總量100質量%為0.3~20質量%。若二烷基矽烷基化合物未達0.1質量%,則由於與有機溶劑中所含之微量水分等發生反應而去活化,故而缺乏形成撥水性保護膜之能力,無法充分地使晶圓表面撥水化。另一方面,於多於50質量%之情形時,擔心以雜質之形式殘留於晶圓表面,另外就成本之觀點而言,亦不佳。
繼而,對本發明之晶圓之洗淨方法進行說明。一般而
言,使用本發明之藥液洗淨之晶圓較多使用經過使晶圓表面成為具有凹凸圖案之面的前處理步驟者。
於上述前處理步驟中,只要可於晶圓表面上形成圖案,則其方法並無限定,作為通常之方法,於晶圓表面上塗佈抗蝕劑後,經由抗蝕劑遮罩而對抗蝕劑進行曝光,蝕刻去除經曝光之抗蝕劑或未經曝光之抗蝕劑,藉此,製作具有所期望之凹凸圖案之抗蝕劑。又,即便藉由對抗蝕劑按壓具有圖案之模型,亦可獲得具有凹凸圖案之抗蝕劑。繼而,對晶圓進行蝕刻。此時,選擇性地蝕刻抗蝕劑圖案之凹部分。若最後剝離抗蝕劑,則獲得具有凹凸圖案之晶圓。
再者,作為上述晶圓,包含矽晶圓;或於矽晶圓表面上形成有含有氧化矽(以下有時表記為SiO2
)、氮化矽(以下有時表記為SiN)等矽元素之膜者;或於形成上述凹凸圖案時,該凹凸圖案之表面含有矽、或氧化矽、氮化矽等矽元素者。
又,對於由含有選自矽、氧化矽、及氮化矽中之至少1種之複數種成分構成之晶圓,亦可於矽元素存在之部分之表面上形成撥水性保護膜。作為由該複數種成分構成之晶圓,亦包含選自矽、氧化矽及氮化矽中之至少1種形成於晶圓表面上者,或於形成凹凸圖案時,於該凹凸圖案之至少凹部表面上形成選自矽、氧化矽、及氮化矽中之至少1種者。進而,亦可為於藍寶石晶圓、各種化合物半導體晶圓、塑膠晶圓等不含矽之晶圓上形成有含有矽之各種膜
者。
本發明係表面上形成有凹凸圖案之晶圓中該凹凸圖案之至少凹部表面含有矽元素之晶圓之洗淨方法,其包括:利用水系洗淨液洗淨上述晶圓表面之水系洗淨液洗淨步驟;於上述晶圓之至少凹部保持撥水性保護膜形成用藥液,且於該凹部表面上形成撥水性保護膜之撥水性保護膜形成步驟;去除晶圓表面之液體之液體去除步驟;及自上述凹部表面去除撥水性保護膜之撥水性保護膜去除步驟。
作為上述水系洗淨液之例,可列舉:水,或水中混合有機溶劑、酸、鹼中之至少1種以上之水作為主成分(例如水之含有率為50質量%以上)者。
於上述水系洗淨時,去除抗蝕劑,去除晶圓表面之顆粒等後,藉由乾燥等去除水系洗淨液時,若凹部之寬度較小、凸部之縱橫比較大,則易於產生圖案倒塌。對凹凸圖案,如圖1及圖2所示進行定義。圖1表示透視表面設為具有凹凸圖案2之面之晶圓1時的示意圖,圖2表示圖1中之a-a'截面之一部分。凹部之寬度5係如圖2所示由凸部3與凸部3之間隔表示,凸部之縱橫比係由凸部之高度6除以凸部之寬度7所得之值表示。洗淨步驟中之圖案倒塌係於凹部之寬度為70nm以下、尤其45nm以下且縱橫比為4以上、尤其6以上時易於產生。
於本發明之晶圓之洗淨方法中,為不發生圖案倒塌而有效地洗淨,較佳為自上述水系洗淨液洗淨步驟起於晶圓之至少凹部總是保持液體之狀態下進行撥水性保護膜形成步驟。又,撥水性保護膜形成步驟之後,於將保持於晶圓之凹部之撥水性保護膜形成用藥液置換成其他液體之情形時,亦較佳為與上述同樣地於晶圓之至少凹部總是保持液體之狀態下進行。再者,於本發明中,只要可將上述水系洗淨液、上述藥液或其他液體保持於晶圓之凹凸圖案之至少凹部,則該晶圓之洗淨方式並無特別限定。作為晶圓之洗淨方式,可列舉一面大致水平地保持晶圓並使其旋轉,一面於旋轉中心附近供給液體而逐片洗淨晶圓之旋轉洗淨為代表之單片方式;或於洗淨槽內浸漬複數片晶圓且將其洗淨之批次方式。再者,作為將上述水系洗淨液、上述藥液或其他液體供給至晶圓之凹凸圖案之至少凹部時的上述水系洗淨液、上述藥液或其他液體之形態,只要保持於該凹部時成為液體,則無特別限定,例如有液體、蒸氣等。
繼而,對撥水性保護膜形成步驟進行說明。自上述水系洗淨液洗淨步驟向撥水性保護膜形成步驟之過渡係藉由於水系洗淨步驟中自保持於晶圓之凹凸圖案之至少凹部之水系洗淨液置換成撥水性保護膜形成用藥液而進行。於自該水系洗淨液置換成撥水性保護膜形成用藥液時,可直接置換,亦可於一次以上置換成不同之洗淨液A(以下有時僅記作「洗淨液A」)後,置換成撥水性保護膜形成用藥液。作為上述洗淨液A之較佳之例,可列舉:水、有機溶劑、水
與有機溶劑之混合物,或者該等之中混合有酸、鹼、界面活性劑中之至少1種以上者等。又,作為上述洗淨液A之較佳例之一種的有機溶劑之例,可列舉:烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、醇類、多元醇之衍生物、含氮化合物溶劑等。
上述撥水性保護膜形成步驟中之撥水性保護膜之形成係藉由將撥水性保護膜形成用藥液保持於晶圓之凹凸圖案之至少凹部而進行。圖3表示由凹部4保持撥水性保護膜形成用藥液8之狀態的示意圖。圖3之示意圖中之晶圓表示圖1之a-a'截面之一部分。於該撥水性保護膜形成步驟時,將撥水性保護膜形成用藥液供給至形成有凹凸圖案2之晶圓1。此時,撥水性保護膜形成用藥液如圖3所示成為保持於至少凹部4之狀態,凹部4之表面經撥水化。再者,本發明之保護膜可不必連續地形成,又,亦可不必均勻地形成,但為可賦予更優異之撥水性,更佳為連續地且均勻地形成。
又,若於保護膜形成步驟中提高藥液之溫度,則易於在更短時間內形成上述保護膜,但有由於撥水性保護膜形成用藥液之沸騰或蒸發等而有損該藥液之穩定性之虞,故而較佳為將上述藥液保持在10~160℃、尤其較佳為15~120℃。
圖4表示液體9保持於經撥水性保護膜形成劑撥水化之凹部4之情形的示意圖。圖4之示意圖中之晶圓表示圖1之a-a'截面的一部分。由撥水性保護膜形成劑而將撥水性保護膜
10形成於凹部4之表面。此時,保持於凹部4之液體9可為上述藥液、自該藥液置換成不同之洗淨液B(以下有時僅記作「洗淨液B」)之液體(洗淨液B),亦可為置換過程中之液體(藥液與洗淨液之混合液)。上述撥水性保護膜10於自凹部4去除液體9時亦保持於晶圓表面。
作為上述洗淨液B之較佳之例,可列舉:水、有機溶劑、水與有機溶劑之混合物,或者該等之中混合有酸、鹼、界面活性劑中之至少1種以上者等。又,作為上述洗淨液B之較佳之例之一種的有機溶劑之例,可列舉:烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、醇類、多元醇類、多元醇類之衍生物、含氮化合物溶劑等。
若將液體保持於上述具有凹凸圖案之晶圓之凹部,則毛細管力於該凹部發揮作用。該毛細管力之大小係根據以下所示之式所求出之P的絕對值。
P=2×γ×cosθ/S(式中,γ為保持於凹部之液體之表面張力,θ為凹部表面與保持於凹部之液體所成之接觸角,S為凹部之寬度)。
若如圖4之凹部4所示於凹部表面上存在撥水性保護膜,則θ增大,P之絕對值下降。就抑制圖案倒塌之觀點而言,較理想為P之絕對值越小越佳,將與所去除之液體之接觸角調整至90°附近,並使毛細管力無限接近0.0MN/m2
。如圖4所示,於凹部表面上形成有保護膜10時,若假設將水保持於該表面時之接觸角為60~120°,則由於難以發生圖案倒塌,故而較佳。由於接觸角越接近90°,作用於該凹
部之毛細管力變得越小,進而越難以發生圖案倒塌,故而尤其較佳為70~110°。
繼而,對上述液體去除步驟進行說明。再者,保持於凹部之液體為上述藥液、洗淨液B、或該藥液與洗淨液B之混合液。作為去除上述液體之方法,較佳為藉由自然乾燥、空氣乾燥、N2
氣體乾燥、旋轉乾燥法、IPA(Isopropyl Alcohol,異丙醇)(2-丙醇)蒸氣乾燥、馬蘭葛尼乾燥、加熱乾燥、溫風乾燥、真空乾燥等眾所周知之乾燥方法而進行。為有效去除上述液體,亦可於排出並去除所保持之液體後,乾燥剩餘液體。
最後,對撥水性保護膜去除步驟進行說明。於去除上述撥水性保護膜之情形時,有效為切斷該保護膜中之C-C鍵、C-F鍵。作為其方法,只要為可切斷上述鍵者,則無特別限定,例如可列舉對晶圓表面進行光照射之方法、加熱晶圓之方法、對晶圓進行臭氧暴露之方法、對晶圓表面進行電漿照射之方法、及對晶圓表面進行電暈放電之方法。
於藉由光照射而去除上述保護膜之情形時,較佳為照射如下紫外線,該紫外線具有較相當於作為該保護膜中之C-C鍵、C-F鍵之鍵能之83kcal/mol、116kcal/mol之能量即340nm、240nm更短之波長。作為該光源,可使用金屬鹵化物燈、低壓水銀燈、高壓水銀燈、準分子燈、碳弧燈等。
又,於藉由光照射而去除上述保護膜之情形時,若藉由
紫外線分解上述保護膜之構成成分,同時產生臭氧,由於該臭氧會使上述保護膜之構成成分氧化揮發,則處理時間縮短,故而尤其較佳。亦可使用低壓水銀燈或準分子燈等作為該光源。又,亦可一面進行光照射一面加熱晶圓。
於加熱晶圓之情形時,較佳為於400~700℃下、較佳為500~700℃下加熱晶圓。較佳為該加熱時間保持1~60分鐘、較佳為10~30分鐘。又,亦可於該步驟中併用臭氧暴露、電漿照射、電暈放電等。又,亦可一面加熱晶圓一面進行光照射。
藉由加熱而去除上述保護膜之方法有使晶圓接觸於熱源之方法、將晶圓放置於利用熱處理爐等加熱之環境中之方法等。再者,由於將晶圓放置於經加熱之環境中之方法即便於處理複數片晶圓之情形時,亦易於對晶圓表面均質地賦予用以去除上述保護膜之能量,故而為操作簡便且於短時間內結束,處理能力較高之工業上有用之方法。
於對晶圓進行臭氧暴露之情形時,可將藉由低壓水銀燈等之紫外線照射或藉由高電壓之低溫放電等中產生之臭氧供給至晶圓表面。亦可一面對晶圓進行臭氧暴露一面進行光照射,亦可進行加熱。
可藉由組合上述之光照射、加熱、臭氧暴露、電漿照射、電暈放電而有效地去除晶圓表面之保護膜。
對於將晶圓之表面設為具有凹凸圖案之面之技術,以其他洗淨液置換保持於凹凸圖案之至少凹部之洗淨液的技
術,為已於其他文獻等中進行各種研究而已經確立之技術,故而於本實施例中,以上述保護膜形成用藥液之評價為中心進行研究。又,如根據先前技術等中敍述之式P=2×γ×cosθ/S(式中,γ為保持於凹部之液體之表面張力,θ為凹部表面與保持於凹部之液體所成之接觸角,S為凹部之寬度)所明確,圖案倒塌較大程度上依賴於洗淨液與晶圓表面之接觸角即液滴之接觸角、及洗淨液之表面張力。於保持於凹凸圖案2之凹部4之洗淨液之情形時,液滴之接觸角與可認為與圖案倒塌等價者之作用於該凹部之毛細管力具有相關性,故而可根據上述式及保護膜10之液滴之接觸角的評價推導出毛細管力。
水滴之接觸角之評價亦如JIS R 3257「基板玻璃表面之濕潤性試驗方法」所揭示,藉由對樣品(基材)表面滴加數μl之水滴,並測定水滴與基材表面所成之角度而進行。然而,於具有圖案之晶圓之情形時,接觸角變得非常大。其原因在於:產生Wenzel效果或Cassie效果,故而接觸角對基材之表面形狀(粗糙程度)造成影響,外觀上水滴之接觸角增大。因此,於表面上具有凹凸圖案之晶圓之情形時,無法準確評價形成於該凹凸圖案表面上之上述保護膜10本身之接觸角。
因此,於本實施例中,將上述藥液供給至表面平滑之晶圓,於晶圓表面上形成保護膜,將該保護膜當作表面上形成有凹凸圖案2之晶圓1之表面所形成之保護膜10,並進行
各種評價。再者,於本實施例中,使用表面平滑之矽晶圓上具有氧化矽層之「附有SiO2
膜之矽晶圓」(表中表記為SiO2
)。
詳情如下所述。以下對供給有保護膜形成用藥液之晶圓之評價方法、該保護膜形成用藥液之調製、並且向晶圓供給該保護膜形成用藥液後之評價結果進行敍述。
進行以下(1)~(3)之評價作為供給有保護膜形成用藥液之晶圓之評價方法。
於形成有保護膜之晶圓表面上放置純水約2μl,並利用接觸角計(協和界面科學製造,CA-X型號)測定水滴與晶圓表面所成之角(接觸角)。雖然保護膜之接觸角越接近90°(毛細感力越無限接近0.0MN/m2
)越有效果,但此處將保護膜之接觸角為60~120°之範圍內者設為合格。
於以下之條件下將低壓水銀燈之UV(Ultraviolet,紫外線)光照射至樣品1分鐘,對撥水性保護膜去除步驟中之保護膜之去除性進行評價。將照射後水滴之接觸角成為10°以下者設為合格(表中表記為A)。
.燈:Sen特殊光源製造之PL2003N-10
.照度:15mW/cm2
(自光源至樣品之距離為10mm)
藉由原子力電子顯微鏡(精工電子製造,SPI3700,2.5
μm見方掃描)而進行表面觀察,求出中心線平均表面粗糙度:Ra(nm)。再者,Ra係將JIS B 0601中定義之中心線平均粗糙度應用於測定面而擴張成三維者,作為「將基準面至指定面之差之絕對值進行平均而獲得的值」,根據以下式而算出。若去除保護膜後之晶圓表面之Ra值為1nm以下,則不會由於洗淨而侵蝕晶圓表面,及上述保護膜之殘渣不存在於晶圓表面,故而設為合格(表中表記為A)。
將作為二烷基矽烷基化合物之四甲基二矽氮烷[(CH3
)2
(H)Si-NH-Si(H)(CH3
)2
]3g、作為有機溶劑之丙二醇單甲醚乙酸酯(PGMEA,Propylene Glycol Monomethyl Ether Acetate)97g加以混合,攪拌約5分鐘,而獲得保護膜形成劑之濃度(以下記作「保護膜形成劑濃度」)相對於保護膜形成用藥液之總量為3質量%之保護膜形成用藥液。
將平滑之附有SiO2
膜之矽晶圓(表面上具有厚度1μm之熱氧化膜層之矽晶圓)浸漬於1質量%之氫氟酸水溶液中2分鐘,繼而,浸漬於純水中1分鐘,並浸漬於2-丙醇中1分鐘。
於20℃下使矽晶圓浸漬於上述「(1)保護膜形成用藥液之調製」中調製之保護膜形成用藥液中1分鐘。其後,將矽晶圓浸漬於2-丙醇中1分鐘,繼而,浸漬於純水中1分鐘。最後,將矽晶圓自純水中取出,吹入空氣而去除表面之純水。
根據上述「供給有保護膜形成用藥液之晶圓之評價方法」中記載之要點對所得之晶圓進行評價,結果如表所示,雖然表面處理前之初始接觸角未達10°,但表面處理後之接觸角變為66°,顯示出撥水性賦予效果。又,UV照射後之接觸角未達10°且可去除保護膜。進而,可確認UV照射後之晶圓之Ra值未達0.5nm,於洗淨時不侵蝕晶圓,進而於UV照射後保護膜之殘渣無殘留。
對實施例1中使用之保護膜形成劑、保護膜形成劑濃度、有機溶劑進行適當變更,並對晶圓進行表面處理,進而對其進行評價。結果示於表1中。再者,於表1中,所謂HFE-7100,意指氫氟醚(住友3M公司製造之Novec HFE-7100),(CH3
)2
(H)Si-Cl意指二甲基氯矽烷。HFE-
7100/PGMEA意指HFE-7100:PGMEA以質量比為95:5之混合溶劑。
除使用六甲基二矽氮烷[(CH3
)3
Si-NH-Si(CH3
)3
]作為保護膜形成劑以外,全部與實施例3相同。評價結果如表所示,表面處理後之接觸角為30°,撥水性賦予效果不充分。
除使用三甲基氯矽烷[(CH3
)3
Si-Cl]作為保護膜形成劑以外,全部與實施例6相同。評價結果如表所示,表面處理後之接觸角為50°,撥水性賦予效果不充分。
實施例3與比較例1除所使用之矽化合物為二甲基矽烷基化合物(實施例3)或三甲基矽烷基化合物(比較例1)之方面以外,條件相同,但相對於實施例3中表面處理後之接觸角為81°且具有非常良好之撥水性賦予效果,比較例1中表面處理後之接觸角為30°且撥水性賦予效果不充分,作為疏水基之甲基之數較少之二甲基矽烷基化合物的撥水性賦予效果較大。實施例6與比較例2之結果亦同樣,相對於二甲基氯矽烷具有良好之撥水性賦予效果,若為三甲基氯矽烷,則未獲得充分之撥水性能。
本發明之保護膜形成用藥液及使用該藥液之晶圓之洗淨方法係於電子產業之積體電路領域中,對元件之製造效率之提高或製造良率之提高有貢獻。
1‧‧‧晶圓
2‧‧‧晶圓表面之凹凸圖案
3‧‧‧圖案之凸部
4‧‧‧圖案之凹部
5‧‧‧凹部之寬度
6‧‧‧凸部之高度
7‧‧‧凸部之寬度
8‧‧‧保持於凹部4之撥水性保護膜形成用藥液
9‧‧‧保持於凹部4之液體
10‧‧‧撥水性保護膜
圖1係表示透視將表面設為具有凹凸圖案2之面之晶圓1時之示意圖。
圖2係表示圖1中之a-a'截面之一部分。
圖3表示由凹部4保持撥水性保護膜形成用藥液8之狀態之示意圖。
圖4係表示形成撥水性保護膜10之凹部4保持液體9之狀態之示意圖。
1‧‧‧晶圓
3‧‧‧圖案之凸部
4‧‧‧圖案之凹部
9‧‧‧保持於凹部4之液體
10‧‧‧撥水性保護膜
Claims (2)
- 一種撥水性保護膜形成用藥液,其係於將表面上具有凹凸圖案且該凹凸圖案之至少凹部表面含有矽元素之晶圓洗淨時,用以於該凹凸圖案之至少凹部表面上形成保護膜者,且含有下述通式[1]所示之二烷基矽烷基化合物,不含有酸及鹼,[化4]R 2 (H)SiX [1] [式中,R分別相互獨立表示選自含有碳數為1~18之烴基之一價有機基、及含有碳數為1~8之氟烷基鏈之一價有機基中的至少1種基,X為選自鹵素基、或-NH-Si(H)R2 ]。
- 一種晶圓之洗淨方法,其係將表面上形成有凹凸圖案之晶圓中該凹凸圖案之至少凹部表面含有矽元素之晶圓洗淨者,且包括:利用水系洗淨液洗淨上述晶圓表面之水系洗淨液洗淨步驟;於上述晶圓之至少凹部保持撥水性保護膜形成用藥液,且於該凹部表面上形成撥水性保護膜之撥水性保護膜形成步驟;去除晶圓表面之液體之液體去除步驟;及自上述凹部表面去除撥水性保護膜之撥水性保護膜去除步驟;且於撥水性保護膜形成步驟中使用如請求項1之撥水性保護膜形成用藥液。
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US9228120B2 (en) * | 2010-06-07 | 2016-01-05 | Central Glass Company, Limited | Liquid chemical for forming protecting film |
JP5586734B2 (ja) * | 2012-08-07 | 2014-09-10 | 東京エレクトロン株式会社 | 基板洗浄装置、基板洗浄システム、基板洗浄方法および記憶媒体 |
JP5543633B2 (ja) * | 2012-11-26 | 2014-07-09 | 東京エレクトロン株式会社 | 基板洗浄システム、基板洗浄方法および記憶媒体 |
JP6375688B2 (ja) * | 2013-05-20 | 2018-08-22 | セントラル硝子株式会社 | 圧送容器、圧送容器を用いた保管方法、及び、圧送容器を用いた移液方法 |
JP6613983B2 (ja) * | 2016-03-23 | 2019-12-04 | Jsr株式会社 | 基板処理方法 |
KR102628534B1 (ko) * | 2016-09-13 | 2024-01-26 | 에스케이하이닉스 주식회사 | 반도체 기판의 처리 방법 |
SG11201908617QA (en) | 2017-03-24 | 2019-10-30 | Fujifilm Electronic Materials Usa Inc | Surface treatment methods and compositions therefor |
EP3704547B1 (en) * | 2017-11-03 | 2022-07-13 | Basf Se | Use of compositions comprising a siloxane-type additive for avoiding pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below |
JP7384332B2 (ja) | 2018-01-05 | 2023-11-21 | フジフイルム エレクトロニック マテリアルズ ユー.エス.エー., インコーポレイテッド | 表面処理組成物及び表面処理方法 |
WO2019159749A1 (ja) * | 2018-02-13 | 2019-08-22 | セントラル硝子株式会社 | 撥水性保護膜形成剤、撥水性保護膜形成用薬液、及びウェハの表面処理方法 |
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