TWI692523B - 具有金屬、電介質及氮化物相容性之抗反射塗層清洗及蝕刻後殘留物移除組成物 - Google Patents
具有金屬、電介質及氮化物相容性之抗反射塗層清洗及蝕刻後殘留物移除組成物 Download PDFInfo
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- TWI692523B TWI692523B TW104118109A TW104118109A TWI692523B TW I692523 B TWI692523 B TW I692523B TW 104118109 A TW104118109 A TW 104118109A TW 104118109 A TW104118109 A TW 104118109A TW I692523 B TWI692523 B TW I692523B
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001475 halogen functional group Chemical group 0.000 claims description 2
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- AGWWTUWTOBEQFE-UHFFFAOYSA-N 4-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NN=C1S AGWWTUWTOBEQFE-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
-
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
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Abstract
本發明係關於一種自其上具有抗反射塗層(ARC)材料及/或蝕刻後殘留物之基板移除該等材料的液體移除組成物及方法。該組成物在積體電路之製造中達成ARC材料及/或蝕刻後殘留物之至少部分移除同時對基板上之金屬物質(諸如鋁、銅及鈷合金)有最小蝕刻,且不會損壞半導體架構中所使用之低k電介質及含氮化物材料。
Description
本發明係關於一種適用於自其上具有抗反射材料及/或蝕刻後殘留物之微電子裝置移除該等材料之液體移除組成物及方法。該液體移除組成物可與下層電介質材料、互連金屬(例如,鋁、銅及鈷合金)、及含氮化物層相容。
當暴露至深紫外(DUV)輻射時,熟知光阻劑之透射率組合基板對DUV波長之高反射率導致DUV輻射反射回至光阻劑中,因而於光阻劑層中產生駐波。駐波於光阻劑中觸發進一步的光化學反應,導致光阻劑之不均勻曝光,包括於不欲暴露至輻射之經遮蔽部分中,其導致線寬、間距、及其他關鍵尺寸的變化。
為解決透射率及反射率的問題,已發展出雙層及三層光阻劑、底部抗反射塗層(BARC)及犧牲抗反射塗層(SARC)。此等塗層係在塗布光阻劑之前塗布至基板。所有此等抗反射塗層皆於典型雙重鑲嵌整合中所遭遇到之晶圓表面上具有平面化效果且皆將UV發色團併入至將會吸收入射UV輻射的旋塗聚合物基質中。
已證實自微電子裝置晶圓乾淨移除抗反射塗層(ARC)材料相當困難及/或成本昂貴。若未經移除的話,該等層將會干擾
隨後的矽化或接點形成。通常,該等層係藉由氧化性或還原性電漿灰化或濕式清洗移除。然而,使基板暴露至氧化性或還原性電漿蝕刻之電漿灰化會藉由改變特徵形狀及尺寸、或藉由增加介電常數而導致損壞電介質材料。後一問題當低k電介質材料(諸如有機矽酸鹽玻璃(OSG)或摻碳氧化物玻璃)係下層電介質材料時更為顯著。因此,通常希望避免使用電漿灰化來移除ARC層。
當在後段製程(BEOL)應用中使用清洗劑/蝕刻劑組成物來處理鋁、銅、鈷合金或其他藉由低電容(低k)絕緣材料或電介質分隔之互連金屬或互連障壁時,用於移除ARC及/或蝕刻後殘留材料之組成物應具有良好的金屬相容性,例如,對銅、鋁、鈷等的低蝕刻速率,且下層矽酸鹽材料保持不受清洗劑組成物影響。水性移除溶液由於較簡單的處置技術通常為較佳,然而,已知水性移除溶液會蝕刻或腐蝕金屬互連體。
因此,技藝中需要可自微電子裝置之表面完全且有效率地移除ARC層及/或蝕刻後殘留物,同時使對共同延伸存在之電介質材料、互連金屬、及/或含氮化物材料的損壞減至最小之具有低水含量的移除組成物。
本發明大致係關於適用於自其上具有抗反射塗層材料及/或蝕刻後殘留物之微電子裝置之表面移除該等材料之液體移除組成物及方法。該液體移除組成物可與低k電介質材料、互連金屬(例如,鋁、銅及鈷合金)、及含氮化物層(例如,氮化矽)相容。
在一態樣中,描述一種液體移除組成物,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、視需
要之水、及介電鈍化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者,其中該液體移除組成物適用於自其上具有抗反射塗層(ARC)材料及/或蝕刻後殘留物之微電子裝置移除該等材料及/或殘留物。
在另一態樣中,一種自其上具有ARC材料及/或蝕
刻後殘留物之微電子裝置移除該等材料及殘留物之方法,該方法包括使微電子裝置與液體移除組成物接觸足夠的時間,以自微電子裝置至少部分移除該材料及殘留物,其中該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、視需要之水、及介電鈍化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者。
本發明之其他態樣、特徵及具體例將可由隨後之揭示內容及隨附之申請專利範圍而更完整明瞭。
本發明涵蓋適用於自其上具有抗反射塗層(ARC)材料及/或蝕刻後殘留物之微電子裝置之表面移除該等材料之液體移除組成物。
為容易參考起見,「微電子裝置」係對應於經製造用於微電子、積體電路、能量收集、或電腦晶片應用中之半導體基板、平板顯示器、相變記憶體裝置、太陽能面板及包括太陽能電池裝置、光伏打元件、及微機電系統(MEMS)的其他產品。應瞭解術語「微電子裝置」不具任何限制意味,且包括任何最終將成為微電子裝置或微電子組件的基板或結構。值得注意地,微電子裝置基板可
為圖案化、毯覆式及/或測試基板。
如本文所用之「蝕刻後殘留物」及「電漿蝕刻後殘留物」係相當於在氣相電漿蝕刻製程(例如,BEOL雙重鑲嵌加工)後殘留的材料。蝕刻後殘留物之性質可為有機、有機金屬、有機矽、或無機,例如,含矽材料、含鈦材料、含氮材料、含氧材料、聚合殘留材料、含銅殘留材料(包括氧化銅殘留物)、含鎢殘留材料、含鈷殘留材料、蝕刻氣體殘留物諸如氯及氟、及其組合。
如本文所定義之「低k電介質材料」及ELK ILD材料係相當於任何在層狀微電子裝置中使用作為電介質材料的材料,其中該材料具有小於約3.5之介電常數。低k電介質材料較佳包括低極性材料諸如含矽有機聚合物、含矽之有機/無機混合材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽、及摻碳氧化物(CDO)玻璃。低k電介質材料最佳係使用有機矽烷及/或有機矽氧烷前驅體沉積。應明瞭低k電介質材料可具有不同密度及不同孔隙度。
如本文所使用之「約」係意指相當於所述值之±5%。
如本文所用,「適用」於自其上具有ARC材料及/或蝕刻後殘留物之微電子裝置移除該等材料係相當於自微電子裝置至少部分移除該ARC及/或蝕刻後殘留材料。較佳地,使用文中所述之組成物自微電子裝置移除至少約90%之材料,更佳至少95%之材料,及最佳至少99%之材料。
如本文所定義之「ARC材料」係相當於雙層及三層光阻劑、底部抗反射塗層(BARC)及犧牲抗反射塗層(SARC)且其性質可為有機及/或無機。
「實質上不含」在本文係定義為小於2重量%,較佳小於1重量%,更佳小於0.5重量%,再更佳小於0.1重量%,及最佳0重量%。
如本文所定義之「含氮化物材料」係相當於氮化矽、氧氮化矽、氮化矽碳、氮化鈦、氧氮化鈦、氮化鉭、及其組合。
本發明之組成物可以如更完整說明於下文之相當多樣的特定配方具體實施。
在所有該等組成物中,當參照包括零下限之重量百分比範圍論述組成物之特定組分時,當明瞭在組成物之各種特定具體例中可存在或不存在此等組分,且在存在此等組分之情況中,其可以基於其中使用此等組分之組成物之總重量計低至0.001重量百分比之濃度存在。
在一態樣中,描述一種適用於自微電子裝置移除ARC層及/或蝕刻後殘留物之液體移除組成物。該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、介電鈍化劑及/或腐蝕抑制劑及/或含矽化合物中至少一者、及視需要之水。
在第一態樣之一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、及至少一種介電鈍化劑,由其所組成,或基本上由其所組成。在另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種介電鈍化劑、及水,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、及至少一種腐蝕抑制劑,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物
包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種腐蝕抑制劑、及水,由其所組成,或基本上由其所組成。在另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、及至少一種含矽化合物,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種含矽化合物、及水,由其所組成,或基本上由其所組成。在另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種介電鈍化劑、及至少一種腐蝕抑制劑,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種介電鈍化劑、至少一種腐蝕抑制劑、及水,由其所組成,或基本上由其所組成。在另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種腐蝕抑制劑、及至少一種含矽化合物,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種腐蝕抑制劑、至少一種含矽化合物、及水,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種介電鈍化劑、及至少一種含矽化合物,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種介電鈍化劑、至少一種含矽化合物、及水,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至
少一種有機溶劑、至少一種腐蝕抑制劑、至少一種介電鈍化劑、及至少一種含矽化合物,由其所組成,或基本上由其所組成。在又另一具體例中,該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種腐蝕抑制劑、至少一種介電鈍化劑、至少一種含矽化合物、及水,由其所組成,或基本上由其所組成。
第一態樣之液體移除組成物具有在約1至約5,更佳低於約4之範圍內的pH值。較佳地,該組成物實質上不含氧化劑(例如,過氧化氫)、氫氧化四級銨化合物、及化學機械拋光研磨劑。
較佳地,該液體移除組成物包括基於組成物之總重量以所指示之重量百分比存在的以下組分,其中組成物之該等組分之重量百分比的總和不超過100重量%。
於一特佳具體例中,水係以在約0.01重量%至約1重量%範圍內之量存在,係去離子且未臭氧化,且係經添加至組成物或殘留存在於其中一種其他組分中。
含氟化物之化合物的適當來源包括,但不限於,氟化氫、氟化銨、氟硼酸、氟化四甲銨(TMAF)及三乙醇胺氫氟酸鹽。或者,可使用氫氟化物之鹽,包括氫氟化銨((NH4)HF2)及氫氟化四烷基銨((R)4NHF2,其中R係甲基、乙基、丙基、丁基、苯基、苄
基、或氟化C1-C4烷基)。本文亦涵蓋兩種或更多種氟化物物質之組合。在一較佳具體例中,該含氟化物之化合物包括氟化氫。值得注意地,氟化氫通常係以含有殘餘量之水運送,因此,儘管其後未故意添加水,移除組成物中亦可能存在水。較佳地,含氟化物之化合物包含氟化氫或氫氟化銨。
有機溶劑物質據認為係充作溶劑且促進可能存在於ARC及/或蝕刻後殘留物中之有機殘留物的溶解。用於此組成物之適宜的溶劑物質包括,但不限於:四亞甲碸;直鏈或分支鏈C1-C6醇,包括,但不限於,甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、第三丁醇、1-戊醇、己醇、環己醇、2-乙基-1-己醇;苯甲醇、呋喃甲醇;二醇類,諸如乙二醇、二甘醇、丙二醇(1,2-丙二醇)、四亞甲二醇(1,4-丁二醇)、2,3-丁二醇、1,3-丁二醇、及新戊二醇;或二醇醚,諸如二甘醇單甲醚、三甘醇單甲醚、二甘醇單乙醚、三甘醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二甘醇單丁醚、三甘醇單丁醚、丙二醇甲基醚、二丙二醇甲基醚、三丙二醇甲基醚、丙二醇正丙基醚、二丙二醇正丙基醚、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、及三丙二醇正丁基醚。其他有用溶劑係典型的極性溶劑諸如二甲基乙醯胺、甲醯胺、二甲基甲醯胺、1-甲基-2-吡咯啶酮、二甲亞碸、四氫呋喃甲醇(THFA)、及其他極性溶劑。本文亦涵蓋兩種或更多種溶劑物質之組合。較佳地,有機溶劑包含1,4-丁二醇、正丁醇、乙二醇、丙二醇、及其組合。
當存在時,腐蝕抑制劑降低對下層中之金屬(例如,銅及/或鈷)的侵蝕。腐蝕抑制劑可為任何適當類型,且可包括,但不限於,苯并三唑(BTA)、1,2,4-三唑(TAZ)、5-胺基四唑(ATA)、
1-羥基苯并三唑、5-胺基-1,3,4-噻二唑-2-硫醇、3-胺基-1H-1,2,4-三唑、3,5-二胺基-1,2,4-三唑、甲苯三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑、1H-四唑-5-乙酸、2-巰基苯并噻唑(2-MBT)、1-苯基-2-四唑啉-5-硫酮、2-巰基苯并咪唑(MBI)、4-甲基-2-苯基咪唑、2-巰基噻唑啉、2,4-二胺基-6-甲基-1,3,5-三、噻唑、咪唑、苯并咪唑、三、甲基四唑、試鉍硫醇I(Bismuthiol I)、1,3-二甲基-2-咪唑啶酮、1,5-五亞甲基四唑、1-苯基-5-巰基四唑、二胺甲基三、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、5-胺基-1,3,4-噻二唑-2-硫醇、苯并噻唑、磷酸三甲苯酯、吲唑、DNA鹼基、吡唑、丙硫醇、抗壞血酸、硫脲、1,1,3,3-四甲基脲、尿素、尿素衍生物、尿酸、乙基黃原酸鉀、甘胺酸、十二烷基苯磺酸(DDBSA)、酒石酸、N,N-二甲基乙醯乙醯胺、1-亞硝基-2-萘酚、聚山梨酸酯80(Tween 80)、十二烷基膦酸(DDPA)、乙二胺四乙酸(EDTA)、(1,2-伸環己基二氮基)四乙酸(CDTA)、二伸乙三胺五乙酸(DTPA)、2-膦醯丁烷-1,2,4-三羧酸(PBTCA)、乙二胺二琥珀酸、及丙二胺四乙酸;膦酸;膦酸衍生物諸如羥基亞乙基二膦酸(HEDP)(Dequest 2010)、1-羥乙烷-1,1-二膦酸、氮基-叁(亞甲基膦酸)(NTMP)、胺基三(亞甲基膦酸)(Dequest 2000)、二伸乙三胺五(亞甲基膦酸)(Dequest 2060S)、乙二胺四(亞甲基膦酸)(EDTMPA)、及其組合。本文亦涵蓋兩種或更多種腐蝕抑制劑之組合。較佳地,腐蝕抑制劑(當存在時)包含DDPA。
介電鈍化劑(當存在時)係經添加來改良液體移除組成物與含氮化物材料之相容性,且包括,但不限於,丙二酸、硼酸、硼酸氫銨、硼酸鹽(例如,五硼酸銨、四硼酸鈉、及硼酸氫銨)、3-羥基-2-萘甲酸、亞胺二乙酸、及其組合。較佳地,介電鈍化劑(當存在時)包含硼酸。
第一態樣之組成物可進一步包括至少一種含矽化合物來降低含氟化物之化合物的活性。在一具體例中,該至少一種含矽化合物包含烷氧矽烷。所涵蓋的烷氧矽烷具有通式SiR1R2R3R4,其中R1、R2、R3及R4係彼此相同或不同且係選自由直鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、分支鏈C1-C6烷基、C1-C6烷氧基(例如,甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基)、苯基、及其組合所組成之群。熟悉技藝人士應明瞭為表徵為烷氧矽烷,R1、R2、R3或R4中之至少一者必需為C1-C6烷氧基。所涵蓋的烷氧矽烷包括甲基三甲氧矽烷、二甲基二甲氧矽烷、苯基三甲氧矽烷、四乙氧矽烷(TEOS)、N-丙基三甲氧矽烷、N-丙基三乙氧矽烷、己基三甲氧矽烷、己基三乙氧矽烷、及其組合。其他可替代烷氧矽烷或在其之外使用的含矽化合物包括六氟矽酸銨、矽酸鈉、矽酸鉀、四甲基矽酸銨(TMAS)、四乙醯氧矽烷、二-第三丁氧二乙醯氧矽烷、乙醯氧甲基三乙氧矽烷、及其組合。較佳地,該含矽化合物包括TMAS。
在各種較佳具體例中,移除組成物係以下列具體例A1-A9調配,其中所有百分比係基於配方之總重量以重量計:
文中所述之液體移除組成物尤其可有效地自微電子裝置基板移除ARC層及/或蝕刻後殘留物,同時對金屬互連物質、低k電介質材料、及/或含氮化物材料有最小損傷。相關金屬包括,但不限於,銅、鎢、鈷、鋁、鉭及釕。較佳地,組成物移除大於95%之ARC材料及/或蝕刻後殘留物且於40℃下具有低於約5埃/分鐘
(Å min-1)之鈷蝕刻速率。
在又另一具體例中,液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、介電鈍化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者、視需要之水、及殘留材料,其中該殘留材料包括ARC及/或蝕刻後殘留物。殘留材料應可溶解及/或懸浮於文中所述之液體移除組成物中。
文中所述之液體移除組成物係經由簡單地添加各別成分及混合至均勻狀態而容易地調配得。此外,可輕易地將液體移除組成物調配為單一包裝配方或在使用點處或使用點前混合的多份配方,例如,可將多份配方之個別份於工具處或於工具上游之儲槽中混合。在本發明之寬廣實務中,各別成分的濃度可在液體移除組成物的特定倍數內寬廣地改變,即更稀或更濃,且當明瞭本發明之液體移除組成物可變化及替代地包含與本文之揭示內容一致之成分的任何組合,由其所組成,或基本上由其所組成。
因此,本發明之另一態樣係關於一種套組,其包括存於一或多個容器中之一或多種適於形成本文所述之組成物的組分。例如,該套組可包括存於一或多個容器中之至少一種含氟化物之化合物、至少一種有機溶劑、及介電鈍化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者,其用於在工廠或使用點處與水結合。或者,該套組可包括存於一或多個容器中之至少一種含氟化物之化合物、及介電鈍化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者,其用於在工廠或使用點處與至少一種溶劑結合。在又另一具體例中,該套組可包括存於一或多個容器中之至少一種含氟化物之化合物、第一有機溶劑、及介電鈍化劑及/或腐蝕
抑制劑及/或至少一種含矽化合物中至少一者,其用於在工廠或使用點處與更多第一有機溶劑及/或第二有機溶劑結合。套組之容器必需適於儲存及運送該液體移除組成物,例如,NOWPak®容器(Advanced Technology Materials,Inc.,Danbury,Conn.,USA)。
容納移除組成物之組分的一或多個容器較佳包括用於使該一或多個容器中之組分流體相通,以進行摻混及配送的構件。舉例來說,參照NOWPak®容器,可對該一或多個容器中之襯裡的外側施加氣體壓力,以導致襯裡之至少一部分的內容物排出,且因此可流體相通而進行摻混及配送。或者,可對習知之可加壓容器的頂部空間施加氣體壓力,或可使用泵於達成流體相通。此外,系統較佳包括用於將經摻混之清洗組成物配送至製程工具的配送口。
較佳使用實質上化學惰性、不含雜質、可撓性及彈性的聚合膜材料,諸如高密度聚乙烯,於製造該一或多個容器的襯裡。理想的襯裡材料不需要共擠塑或障壁層來進行加工,且不含任何會不利影響待置於襯裡中之組分之純度需求的顏料、UV抑制劑、或加工劑。理想襯裡材料的清單包括含純粹(無添加劑)聚乙烯、純粹聚四氟乙烯(PTFE)、聚丙烯、聚胺基甲酸酯、聚二氯亞乙烯、聚氯乙烯、聚縮醛、聚苯乙烯、聚丙烯腈、聚丁烯等等的膜。此等襯裡材料的較佳厚度係在約5密爾(mil)(0.005英吋)至約30密爾(0.030英吋)之範圍內,例如,20密爾(0.020英吋)之厚度。
關於套組之容器,將以下專利及專利申請案之揭示內容的各別全體併入本文為參考資料:美國專利第7,188,644號,標
題「使超純液體中之顆粒產生減至最小的裝置及方法(APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)」;美國專利第6,698,619號,標題「可回收及再利用的桶中袋流體儲存及配送容器系統(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM)」;及2007年5月9日以John E.Q.Hughes之名義提出申請之美國專利申請案第60/916,966號,標題「材料摻混及分佈用的系統及方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION)」;及2008年5月9日以Advanced Technology Materials,Inc.之名義提出申請之PCT/US08/63276,標題「材料摻混及分佈用的系統及方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION)」。
在移除應用中,移除組成物係以任何適當方式施用至待清洗之微電子裝置,例如,經由將移除組成物噴塗於微電子裝置之表面上,經由將微電子裝置浸泡於一定量之清洗組成物中,經由使待清洗之微電子裝置與經移除組成物飽和之另一材料(例如,墊、或纖維吸收性塗布器元件)接觸,經由使微電子裝置與循環的移除組成物接觸,或藉由任何其他藉以使移除組成物與待清洗之微電子裝置進行移除接觸之適當手段、方式或技術。
當應用至半導體製造操作時,文中所述之液體移除組成物可有效用於自其上具有ARC及/或蝕刻後殘留材料之微電子裝置結構移除該等材料。該等移除組成物藉由其針對該等ARC材料及/或蝕刻後殘留材料相對於其他可能存在於微電子裝置上且
暴露至移除組成物之材料(諸如低k電介質結構、金屬化、障蔽層等)的選擇性,以高度有效率的方式達成ARC及/或蝕刻後殘留材料的至少部分移除。此外,該等移除組成物具有低含量的水,例如,低於約1重量百分比,因此,其可與諸如銅、鋁及鈷的金屬互連層相容。在本發明組成物存在下之銅及/或鈷蝕刻速率較佳低於5埃/分鐘,更佳低於2埃/分鐘,最佳低於1埃/分鐘。
在使用移除組成物於自其上具有ARC材料及/或蝕刻後殘留物之微電子裝置基板移除該等材料時,典型上使該組成物與裝置基板在約20℃至約80℃範圍內之溫度下接觸約1至約60分鐘,較佳約20至約30分鐘之時間。該等接觸時間及溫度係為說明性,可使用任何其他可有效地自裝置基板至少部分地移除ARC材料及/或蝕刻後殘留物之適宜時間及溫度條件。如本文所定義,「至少部分移除」係相當於移除至少50%之ARC材料及/或蝕刻後殘留物,較佳移除至少80%。最佳地,使用文中所述之液體移除組成物移除至少90%之ARC材料及/或蝕刻後殘留物。
於達成期望的清洗作用後,可輕易地將移除組成物自其先前經施用的裝置移除,例如,藉由沖洗、洗滌、或其他移除步驟,此可能係在文中所述組成物之指定最終應用中所需且有效。舉例來說,可使用去離子水沖洗裝置。
又再一具體例係關於製造包含微電子裝置之物件的方法,該方法包括使微電子裝置與液體移除組成物接觸足夠的時間,以自其上具有ARC及/或蝕刻後殘留材料之微電子裝置移除該等材料,及將該微電子裝置併入至該物件中,其中該液體移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、介電鈍
化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者、及視需要之水。在本發明組成物存在下之低k電介質及/或氮化物蝕刻速率較佳低於5埃/分鐘,更佳低於2埃/分鐘,最佳低於1埃/分鐘。
另一態樣係關於一種包含移除組成物、微電子裝置晶圓、及ARC材料及/或蝕刻後殘留物的製造物件,其中該移除組成物包含至少一種含氟化物之化合物、至少一種有機溶劑、介電鈍化劑及/或腐蝕抑制劑及/或至少一種含矽化合物中至少一者、及視需要之水。
本發明之特徵及優點由以下論述的說明性實施例作更完整展示。
製備包含至少一種含氟化物之化合物(即HF,其含有自然存在水)、至少一種有機溶劑、及至少一種介電鈍化劑之移除組成物及測定TiON(於20分鐘時)及SiN(於60分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5分鐘時)。該等實驗皆係於35℃下進行。使用TiON之蝕刻速率來模擬含Ti殘留物及因此其自表面之移除。結果提供於下表1。
可看見包含鈍化劑使氮化矽蝕刻速率相對於對照組(配方A)減低,但總體效能亦取決於含氟化物之化合物的濃度。在各情況中,5分鐘時之TiN蝕刻速率係低於0.5埃/分鐘,及30分鐘時之W蝕刻速率係低於0.5埃/分鐘。
製備包含至少一種含氟化物之化合物、至少一種有機溶劑、及至少一種介電鈍化劑及/或至少一種腐蝕抑制劑之移除組成物及測定TiON(於20分鐘時)及SiN(於30分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5分鐘時)。除非另外指明,否則該等實驗皆係於40℃下進行。使用TiON之蝕刻速率來模擬含Ti殘留物及因此其自表面之移除。結果提供於下表2。
DDBSA=十二烷基苯磺酸
TA=酒石酸
DMA=N,N-二甲基乙醯乙醯胺
NN=1-亞硝基-2-萘酚
Bis=試鉍硫醇
DDPA=十二烷基膦酸
CDTA=(1,2-伸環己基二氮基)四乙酸
DTPA=二伸乙三胺五乙酸
HEDP=羥基亞乙基二膦酸
NTMP=氮基-叁(亞甲基膦酸)
可看見DDPA係彼等受測試者中最有效的腐蝕抑制劑,儘管若干其他者可有效地使SiN移除以及鈷損耗最小化。腐蝕抑制劑之存在促進Co損耗之降低同時並維持清洗能力。
製備包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種腐蝕抑制劑、及至少一種含矽化合物之移除組成物及測定TiON(於20分鐘時)及SiN(於30分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5分鐘時)。該等實驗皆係於40℃下進行。結果提供於下表3。
可看見TMAS有助於保護SiN,與當存在介電鈍化劑時所觀察到者相似。
製備包含至少一種含氟化物之化合物、至少一種有機溶劑、至少一種介電鈍化劑、及至少一種腐蝕抑制劑之移除組成物及測定TiON(於20分鐘時)及SiN(於60分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5分鐘時)。該等實驗皆係於40℃下進行。結果提供於下表4。
可看見存在介電鈍化劑(即硼酸)對使鈷損耗及氮化矽蝕刻速率減至最小有最大的影響。
製備包含至少一種含氟化物之化合物、丙二醇(PG)、及至少一種介電鈍化劑及/或至少一種腐蝕抑制劑及/或至少一種含矽化合物之移除組成物及測定TiON(於20分鐘時)及SiN(於30分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5分鐘時)。該等實驗皆係於40℃下進行。結果提供於下表5。
應注意,配方AE於45℃下可與Co及SiN相容,而不會犧牲清洗效力。
製備包含0.25重量%氟化氫銨、29.25重量%正丁醇、乙二醇(EG)、至少一種介電鈍化劑及/或至少一種腐蝕抑制劑之移除組成物及測定TiON(於20分鐘時)及SiN(於60分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5分鐘時)。該等實驗皆係於35℃下進行。結果提供於下表6。
可看見硼酸改良SiN相容性及DDPA/Tween 80組合幫助減小起始Co損耗。
製備包含至少一種含氟化物之化合物、29.250正丁醇、及至少一種額外有機溶劑之移除組成物及測定TiON(於20分鐘時)及SiN(於60分鐘時)之蝕刻速率以及自鈷試樣的鈷損耗(於5
分鐘時)。該等實驗皆係於35℃下進行。結果提供於下表7。
可看見起始Co損耗隨TMAF之量增加而減小,且隨作為額外有機溶劑之EG再進一步地減小。SiN蝕刻速率隨蝕刻劑更換而顯著地減小。
因此,雖然本發明已參照本發明之特定態樣、特徵及說明具體例說明於文中,但當明瞭本發明之效用並不因此受限,而係可延伸至涵蓋許多其他態樣、特徵及具體例。因此,後文陳述之申請專利範圍意欲相應地經廣泛解釋為包括在其精神及範疇內的所有此等態樣、特徵及具體例。
Claims (10)
- 一種液體移除組成物,其包含約0.01重量%至約25重量%之至少一種含氟化物之化合物、約0.01重量%至約99.9重量%之至少一種有機溶劑、約0.01重量%至約10重量%之水、約0.01重量%至約20重量%之至少一種腐蝕抑制劑、及約0.01重量%至約2重量%之至少一種介電鈍化劑及/或至少一種含矽化合物,其中該液體移除組成物適用於自其上具有抗反射塗層(ARC)材料及/或蝕刻後殘留物之微電子裝置移除該等材料及/或殘留物。
- 如申請專利範圍第1項之液體移除組成物,其包含至少一種介電鈍化劑,其中該介電鈍化劑包括選自由下列所組成之群之物質:丙二酸、硼酸、硼酸氫銨、五硼酸銨、四硼酸鈉、硼酸氫銨、3-羥基-2-萘甲酸、亞胺二乙酸、及其組合。
- 如申請專利範圍第1項之液體移除組成物,其中該腐蝕抑制劑包括選自由下列所組成之群之物質:苯并三唑(BTA)、1,2,4-三唑(TAZ)、5-胺基四唑(ATA)、1-羥基苯并三唑、5-胺基-1,3,4-噻二唑-2-硫醇、3-胺基-1H-1,2,4-三唑、3,5-二胺基-1,2,4-三唑、甲苯三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑、1H-四唑-5-乙酸、2-巰基苯并噻唑(2-MBT)、1-苯基-2-四唑啉-5-硫酮、2-巰基苯并咪唑(MBI)、4-甲基-2-苯基咪唑、2-巰基噻唑啉、2,4-二胺基-6-甲基-1,3,5-三苊、噻唑、咪唑、苯并咪唑、三苊、甲基四唑、試鉍硫醇I(Bismuthiol I)、1,3-二甲基-2-咪唑啶 酮、1,5-五亞甲基四唑、1-苯基-5-巰基四唑、二胺甲基三苊、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、5-胺基-1,3,4-噻二唑-2-硫醇、苯并噻唑、磷酸三甲苯酯、吲唑、DNA鹼基、吡唑、丙硫醇、抗壞血酸、硫脲、1,1,3,3-四甲基脲、尿素、尿素衍生物、尿酸、乙基黃原酸鉀、甘胺酸、十二烷基苯磺酸(DDBSA)、酒石酸、N,N-二甲基乙醯乙醯胺、1-亞硝基-2-萘酚、聚山梨酸酯80(Tween 80)、十二烷基膦酸(DDPA)、乙二胺四乙酸(EDTA)、(1,2-伸環己基二氮基)四乙酸(CDTA)、二伸乙三胺五乙酸(DTPA)、2-膦醯丁烷-1,2,4-三羧酸(PBTCA)、乙二胺二琥珀酸、丙二胺四乙酸;膦酸;羥基亞乙基二膦酸(HEDP)(Dequest 2010)、1-羥乙烷-1,1-二膦酸、氮基-叁(亞甲基膦酸)(NTMP)、胺基三(亞甲基膦酸)(Dequest 2000)、二伸乙三胺五(亞甲基膦酸)(Dequest 2060S)、乙二胺四(亞甲基膦酸)(EDTMPA)、及其組合。
- 如申請專利範圍第1項之液體移除組成物,其包含至少一種含矽化合物,其中該含矽化合物包括選自由下列所組成之群之物質:甲基三甲氧矽烷、二甲基二甲氧矽烷、苯基三甲氧矽烷、四乙氧矽烷(TEOS)、N-丙基三甲氧矽烷、N-丙基三乙氧矽烷、己基三甲氧矽烷、己基三乙氧矽烷、六氟矽酸銨、矽酸鈉、矽酸鉀、四甲基矽酸銨(TMAS)、四乙醯氧矽烷、二-第三丁氧二乙醯氧矽烷、乙醯氧甲基三乙氧矽烷、及其組合。
- 如申請專利範圍第1至4項中任一項之液體移除組成物,其中,該至少一種有機溶劑包括選自由下列所組成之群之化合物:四亞甲碸、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、第三丁醇、1-戊醇、己醇、環己醇、2-乙基-1-己醇、苯甲醇、呋喃甲醇、 乙二醇、二甘醇、丙二醇(1,2-丙二醇)、四亞甲二醇(1,4-丁二醇)、2,3-丁二醇、1,3-丁二醇、新戊二醇、二甘醇單甲醚、三甘醇單甲醚、二甘醇單乙醚、三甘醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二甘醇單丁醚、三甘醇單丁醚、丙二醇甲基醚、二丙二醇甲基醚、三丙二醇甲基醚、丙二醇正丙基醚、二丙二醇正丙基醚、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、及三丙二醇正丁基醚、二甲基乙醯胺、甲醯胺、二甲基甲醯胺、1-甲基-2-吡咯啶酮、二甲亞碸、四氫呋喃甲醇(THFA)、及其組合。
- 如申請專利範圍第1至4項中任一項之液體移除組成物,其中,該至少一種有機溶劑包括選自由下列所組成之群之化合物:1-丁醇、1,4-丁二醇、及其組合。
- 如申請專利範圍第1至4項中任一項之液體移除組成物,其中,該至少一種有機溶劑包括丙二醇。
- 如申請專利範圍第1至4項中任一項之液體移除組成物,其中,該組成物包含水,且其中水係基於組成物之總重量以約0.01重量%至約1重量%之量存在。
- 如申請專利範圍第1至4項中任一項之液體移除組成物,其中,該至少一種含氟化物之化合物包括選自由下列所組成之群之物質:氟化氫、氟化銨、氟硼酸、氟化四甲銨(TMAF)、三乙醇胺氫氟酸鹽、氫氟化銨((NH4)HF2)、氫氟化四烷基銨((R)4NHF2)、及其組合。
- 一種自其上具有ARC材料及/或蝕刻後殘留物之微電子裝置移除該等材料及殘留物之方法,該方法包括使該微電子裝置與液 體移除組成物接觸足夠的時間,以自該微電子裝置至少部分移除該等材料及殘留物,其中該液體移除組成物包含約0.01重量%至約25重量%之至少一種含氟化物之化合物、約0.01重量%至約99.9重量%之至少一種有機溶劑、約0.01重量%至約10重量%之水、約0.01重量%至約20重量%之至少一種腐蝕抑制劑、及約0.01重量%至約2重量%之至少一種介電鈍化劑及/或至少一種含矽化合物。
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