TWI394820B - 化學機械研磨用組成物及其相關方法 - Google Patents
化學機械研磨用組成物及其相關方法 Download PDFInfo
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- TWI394820B TWI394820B TW094121113A TW94121113A TWI394820B TW I394820 B TWI394820 B TW I394820B TW 094121113 A TW094121113 A TW 094121113A TW 94121113 A TW94121113 A TW 94121113A TW I394820 B TWI394820 B TW I394820B
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- Prior art keywords
- acid
- composition
- weight
- copolymer
- methacrylic
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- 239000002184 metal Substances 0.000 claims description 43
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
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- 239000003139 biocide Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 101150089254 epd2 gene Proteins 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000019314 gum ghatti Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
- H01L21/04—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
- 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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係有關半導體晶圓材料的化學機械平坦化(又稱為化學機械研磨，簡稱CMP)，更特定而言，有關在介電質和障壁材料的存在下研磨半導體晶圓上的金屬互連(metal interconnects)之CMP組成物和方法。
典型地，半導體晶圓為具有介電層的矽晶圓，該介電層含有多個溝槽，此等溝槽被排列成介電層內做為電路互連(circuit interconnects)的圖案。該圖案排列通常具有鑲嵌結構(damascene structure)或雙重鑲嵌結構(dual damascene structure)。一障壁層覆蓋著該經圖案化的介電層且一金屬層覆蓋著該障壁層。該金屬層的厚度至少足以用金屬填滿該經圖案化的溝槽而形成電路互連。
CMP程序常包括多重研磨步驟。例如，第一步驟係以起始高速率下移除過多的互連金屬，例如銅。於第一步驟移除之後，第二步驟研磨可能移除保留在互連金屬外面的障壁層上之金屬。隨後的研磨係從半導體晶圓的底層介電層(underlying dielectric layer)移除掉障壁層以在介電層和金屬互連上面提供一平坦的研磨表面。
半導體基板上面的溝或槽內的金屬提供形成金屬電路的金屬線。要解決的問題之一為研磨操作傾向於從每一溝或槽中移除掉金屬，造成此等金屬的凹陷淺碟效應(dishing)。淺碟效應係不合宜者，因為其會造成金屬電路
之關鍵尺寸(critical dimension)變異。為了減低淺碟效應，乃在較低的研磨壓力下實施研磨。不過，單只減低研磨壓力，研磨將需要持續一段延長的時間。而於整個延長期間，仍會繼續產生淺碟效應。本技藝所需者為一種減低溝或槽內的金屬之淺碟效應而不會延長研磨操作的持續期。在第二步驟短時間研磨之後，清除留在表面之互連金屬殘渣之研磨組成物亦為本技藝所需。
美國專利第6,632,259號述及經設計的共聚物在CMP用水性研磨組成物上的用途。此等包括從丙烯酸單體對甲基丙烯酸單體之莫耳比例為約1：20至約20：1的丙烯酸單體與甲基丙烯酸單體之混合物所衍生的共聚物。曾揭示將此等用於不包括改質纖維素的研磨組成物中。
於第一樣態中，本發明提供一種含有金屬之半導體晶圓之化學機械研磨用水性組成物，其包括氧化劑、非鐵質金屬的抑制劑、非鐵質金屬的錯合劑、改質纖維素、0.01至5重量%的丙烯酸和甲基丙烯酸之共聚物，及餘量的水；其中該丙烯酸和甲基丙烯酸之共聚物的(丙烯酸/甲基丙烯酸)單體比例在1：30至30：1範圍內，且該共聚物的分子量在1K至1000K範圍內。該研磨組成物視需要可含有高達3重量%的研磨劑(abrasive)。
於第二樣態中，本發明提供一種化學機械研磨含有金屬之半導體晶圓之方法，其包括a)將該晶圓與一研磨組成物接觸，該研磨組成物包括氧化劑、非鐵質金屬的抑制
劑、非鐵質金屬的錯合劑、改質纖維素、0.01至5重量%的丙烯酸和甲基丙烯酸之共聚物，及餘量的水；其中該丙烯酸和甲基丙烯酸之共聚物的(丙烯酸/甲基丙烯酸)單體比例在1：30至30：1範圍內，且該共聚物的分子量在1K至1000K範圍內；及b)使用研磨墊研磨該晶圓。該研磨組成物視需要可含有高達3重量%的研磨劑(abrasive)。
該組成物和方法可以在對半導體晶圓施予CMP之時提供良好的金屬移除速率和足夠的金屬清空而不會發生金屬互連的過份淺碟化。本發明組成物係利用丙烯酸和甲基丙烯酸之水溶性共聚物以及以羧酸官能基改質之水溶性纖維素。雖然本發明在銅互連中具有特別的用處，不過本發明水性研磨組成物對於其他的非鐵質金屬互連，例如鋁、金、鎳、鉑族金屬、銀、鎢、和彼等的合金也能提供增強的研磨。
本發明共聚物係將丙烯酸單體和甲基丙烯酸單體以1：30至30：1，較佳約1：9至9：1，最佳約2：3之莫耳比例而合成者。本發明共聚物之分子量在1K至1000K範圍內；較佳者在20K至200K範圍內。就本說明書的目的言之，分子量係指重量平均分子量。
本發明研磨組成物含有水可溶的以羧酸官能基改質過的纖維素。較佳者，該組成物含有0.01至5.0重量%的水溶性纖維素。最佳者，該組成物含有約0.3重量%的水溶
性纖維素。範例改質纖維素為陰離子性樹膠類例如瓊脂膠、阿拉伯膠、哥地膠(ghatti gum)、刺梧桐膠(karaya gum)、古亞膠(guar gum)、果膠、刺槐豆膠(locust bean gum)、黃蓍膠(tragacanth gum)、羅望子膠(tamarind gum)、鹿角菜膠(carrageenan gum)、和黃原膠(xantham gum)、改質澱粉、海藻酸、甘露糖醛酸、葛蘿酸(guluronic acid)、和彼等的改質物和組合。較佳的水溶性纖維素，羧甲基纖維素(CMC)，具有0.1至3.0的取代度，與1K至1000K的分子量。更佳的CMC具有0.7至1.2的取代度，與40K至250K的分子量。CMC中的取代度為在纖維素分子內每一無水葡萄糖單位上經取代的羥基數目。其可以視為CMC中所含羧酸基的“密度”之量度。
較佳者，該溶液包含高達25重量%的氧化劑。更佳者，該氧化劑的含量為在5至10重量%的範圍之內。該氧化劑於低pH範圍下，在促進該溶液移除銅上特別有效。該氧化劑可為許多種氧化性化合物中的至少一者，例如過氧化氫(H2
O2
)、單過硫酸鹽(monopersulfates)、碘酸鹽類、過酞酸鎂、過乙酸、和其他過酸類、過硫酸鹽類、溴酸鹽類、過碘酸鹽類、硝酸鹽類、鐵鹽類、鈰鹽類、Mn(III)、Mn(IV)和Mn(VI)鹽類、銀鹽類、銅鹽類、鉻鹽類、鈷鹽類、鹵素、次氯酸鹽類和彼等的混合物。再者，常為有利者為使用氧化性化合物的混合物。當研磨液(polishing slurry)含有不安定性氧化劑例如，過氧化氫之時，常為最有利者為在使用當時將氧化劑混合到組成物之內。
另外，該容液含有抑制劑以控制經由靜態蝕刻或其他移除機制的銅互連移除速率。調整抑制劑的濃度可經由保護金屬使其免於被靜態蝕刻而調整互連金屬移除速率。較佳者，該溶液含有0.05至5.0重量%的抑制劑。最佳者，該溶液含有0.2至1.0重量%的抑制劑。該抑制劑可以由抑制劑之混合物所構成。唑類抑制劑對於銅和銀互連特別有效。典型的唑類抑制劑包括苯并三唑(BTA)、氫硫基苯并噻唑(MBT)、甲苯基三唑(TTA)和咪唑。BTA對銅和銀係最為有效的抑制劑。
除了抑制劑之外，該組成物較佳地包含非鐵質金屬的錯合劑。該錯合劑有助於金屬膜，例如銅的移除速率。較佳者，該組成物含有0.01至15重量%非鐵質金屬的錯合劑。最佳者，該組成物含有0.1至1重量%非鐵質金屬的錯合劑。範例錯合劑包括乙酸、檸檬酸、乙醯乙酸乙酯、乙醇酸、乳酸、蘋果酸、草酸、水楊酸、二硫代胺基甲酸二乙基酯鈉、丁二酸、酒石酸、氫硫基乙酸、甘胺酸、丙胺酸、天冬胺酸、乙二胺、三甲基二胺、丙二酸、戊二酸(glutaric acid)、3-羥基丁酸、丙酸、酞酸、異酞酸、3-羥基水楊酸、3,5-二羥基水楊酸、五倍子酸、葡萄糖酸、焦兒茶酚、焦棓酚(pyrogallol)、鞣酸、包括，彼等的鹽類和混合物。較佳者，該錯合劑係選自乙酸、檸檬酸、乙醯乙酸乙酯、乙醇酸、乳酸、蘋果酸、草酸和彼等的混合物所構成的群組。最佳者，該錯合劑為蘋果酸。
該等化合物在以水調整總量溶液中，在廣闊pH範圍
內皆可提供效力。此溶液的有用pH範圍從2延展到至少5。此外，該溶液較佳者係依賴其餘的去離子水來限制意外的雜質。本發明研磨流體的pH較佳者為從2.5至4.2，更佳者為具有2.6至3.8的pH。調整本發明組成物所具pH值所用的酸為，例如，硝酸、硫酸、鹽酸、磷酸和類似者。調整本發明組成物所具pH值所用的範例鹼為，例如，氫氧化銨和氫氧化鉀。
另外，該研磨組成物可以視需要包含高達3重量%的研磨劑以促進金屬層的移除。在此範圍之內，宜於使研磨劑的含量低於或等於1重量%。最佳者，本發明研磨組成物不含研磨劑。
該研磨劑具有小於或等於500奈米(nm)之平均粒子尺寸以防止過度的金屬淺碟效應和介電質侵蝕(dielectric erosion)及改進平坦化。就此說明書之目的言之，粒子尺寸係指研磨劑的平均粒子尺寸。更佳者，宜於使用具有小於或等於100奈米的平均粒子尺寸之膠體研磨劑。再者，使用具有小於或等於70奈米的平均粒子尺寸之膠體氧化矽時所發生的介電質侵蝕和金屬淺碟效應會減低。此外，較佳的膠體研磨劑可包括添加劑，例如分散劑、界面活性劑、緩衝劑、和殺生物劑以改進膠體研磨劑的穩定性。一種此等膠體研磨劑為得自Clariant S.A.，或Puteaux,France的膠體氧化矽。此外，也可以利用其他的研磨劑，包括經發煙、沉澱、聚集等處理者。
該研磨組成物可以包括將金屬互連層“機械地”移除所
用的研磨劑。範例磨蝕劑包括無機氧化物、無機氫氧化物、無機氫氧化物氧化物、金屬硼化物、金屬碳化物、金屬氮化物、聚合物粒子與包括至少一種前述物質之混合物。適當的無機氧化物包括，例如，氧化矽(SiO2
)、氧化鋁(Al2
O3
)、氧化鋯(ZrO2
)、氧化鈰(CeO2
)、氧化錳(MnO2
)、氧化鈦(TiO2
)或包括至少一種前述氧化物之組合。適當的無機氫氧化物氧化物包括，例如，鋁氫氧化物氧化物(“水鋁石”(boehmite))。於需要時也可以利用此等無機氧化物的改質形式，例如經有機聚合物塗覆的無機氧化物粒子和無機物塗覆的粒子。適當的金屬碳化物、硼化物、和氮化物包括，例如，碳化矽、氮化矽、碳氮化矽(SiCN)、碳化硼、碳化鎢、碳化鋯、硼化鋁、碳化鉭、碳化鈦、或包括至少一種前述金屬碳化物、硼化物、和氮化物的組合。於需要時也可以利用鑽石作為研磨劑。或者研磨劑也包括聚合物粒子、經塗覆之聚合物粒子、和經界面活性劑穩定化的粒子。若使用研磨劑，則研磨劑以氧化矽為較佳。
本發明組成物可應用於包含導電性金屬，例如銅、鋁、鎢、鉑、鈀、金、或銥；障壁層或襯膜，例如鉭、氮化鉭、鈦、或氮化鈦；與底層介電層之任何半導體晶圓。為本說明書之目的，術語“介電質”係指具有介電常數k的半導電性材料，其包括低-k和超低-k介電材料。該組成物和方法可以優良地用來防止多重晶圓結構，例如，多孔型和非多孔型低-k介電質、有機和無機低-k介電質、有機矽酸鹽玻璃(OSG)、氟矽酸鹽玻璃(FSG)、碳摻雜氧化物(CDO)、原
矽酸四乙基酯(TEOS)和衍生自TEOS的氧化矽等之侵蝕。本發明組成物也可以用於ECMP(電化學機械研磨)。
為要製造高分子量(~200,000 MW)的AA/MAA(2：3莫耳比)共聚物時，係使用75克AA 100%丙烯酸、135克MAA 100%甲基丙烯酸、0.5克+1.9克NaPS Na2
S2
O8
、MW=238.1、270克+42克+380克去離子(DI)水、和20克50%NaOH。將25克混合單體倒入到4頸2000-毫升反應器之內，接著倒入270克去離子水和0.5克過硫酸鈉。將混合物加熱到高達92℃，然後將其餘的混合單體與1.9克過硫酸鈉在42克水中的溶液共同倒入到反應器內40和50分鐘。將反應混合物在92℃下再保持1小時，然後冷卻到室溫。檢驗粗產物的GC和GPC且使用50% NaOH溶液中和掉10%的酸。此步驟得到Mw/Mn=198,000/30,000，AA=532 ppm，MAA=38 ppm，pH=3.7，粗產物的固體含量%為45.6%。使用20克的50% NaOH和380克的水將粗產物稀釋到24.45%，將800克的粗產物進一步稀釋到10%溶液。
要製造低分子量(~27,000)的AA/MAA(2：3莫耳比)共聚物時，係使用179克AA(100%丙烯酸)、321克MAA(100%甲基丙烯酸)、23.4克NaPS(Na2
S2
O8
)、815克+110克去離子(DI)水、和49.7克50%NaOH溶液。將25克混合單體倒入到4頸2000毫升反應器之內，接著給入815克去離子水和2.4克過硫酸鈉。將混合物加熱到95℃，然後將
其餘的混合單體與21克過硫酸鈉在110克水中的溶液分別經140和160分鐘同時倒入反應器內。將反應混合物在92℃下再保持1小時，然後冷卻到室溫。使用49.7克的50% NaOH中和掉10%的酸。此步驟得到Mw/Mn=30860/6656，AA=0 ppm，MAA=47 ppm，pH=1.2。使用49.7克的50% NaOH將粗產物中和到pH=3.6。最後固體含量%=37.8%。
於實施例中，所有組成物，以重量%計，都含有0.50% BTA、0.22%蘋果酸、0.32%羧甲基纖維素(CMC)和9.00%過氧化氫，pH為2.8。
實驗係於中等下壓壓力(down force pressure)下測量銅研磨速率及測定從半導體晶圓的殘留銅之清空。尤其，該試驗係測定在丙烯酸和甲基丙烯酸之共聚物的存在中利用改質纖維素化合物對於研磨速率、清空時間、和殘留銅清空之影響。清空時間係經定義為EPD2-EPD1，此處EPD1為偵測到透過銅層的第一障壁層跡象時之起始終點偵測時間。EPD2為偵測器只看到障壁層之偵測時間。第1圖以圖形顯示出清空時間的此種定義。一裝有ISRM偵測器系統的Applied Materials,Inc.Mirra 200毫米研磨機，使用IC1010TM
聚胺基甲酸酯研磨墊(Rohm and Haas Electronic Materials CMP Inc.)於至少約2 psi(13.8 kPa)的下壓力、150立方厘米/分鐘的研磨溶液流率、80 RPM的壓盤速度、和40 RPM的載體速度等條件下將樣品平坦化。研磨溶液具有使用以硝酸調整過的pH值。所有的溶液都含有去離
子水。
如表1中所示者，以0.1重量%的量添加丙烯酸對甲基丙烯酸莫耳比為2：3之共聚物，可提供最佳的銅移除速率及殘留銅清空且淺碟效應低。淺碟效應結果為在一200毫米Sematech 854光罩TEOS晶圓上面形成於中心和於90%/100微米邊緣位置的階高平均值ASH(average of step hight)。雖然在大部份樣品都發現某些殘留銅，不過所有的清空時間都少於30秒鐘。
第1圖為清空時間(clear time)的圖解說明。
Claims (8)
- 一種含金屬之半導體晶圓之化學機械研磨(CMP)用水性組成物，該組成物包括0至25重量%的氧化劑、0.05至1重量%的銅抑制劑、0.01至15重量%的銅錯合劑、0.01至5重量%的改質纖維素(該改質纖維素具有羧酸官能基及界於1,000與250,000之間的分子量)、0.01至5重量%的丙烯酸和甲基丙烯酸之共聚物，及餘量的水；其中該丙烯酸和甲基丙烯酸之共聚物的(丙烯酸/甲基丙烯酸)單體比例在1：30至30：1範圍內，且該共聚物之分子量在1,000至1,000,000範圍內，其中該銅錯合劑係選自乙酸、檸檬酸、乙醇酸、乳酸、蘋果酸、草酸、水楊酸、丁二酸、酒石酸、氫硫基乙酸、甘胺酸、丙胺酸、天冬胺酸、乙二胺、三甲基二胺、丙二酸、戊二酸、3-羥基丁酸、丙酸、酞酸、異酞酸、3-羥基水楊酸、3,5-二羥基水楊酸、五倍子酸、葡萄糖酸、焦兒茶酚、焦棓酚、鞣酸、包括彼等的鹽類和混合物、二硫代胺基甲酸二乙基酯鈉、乙醯乙醇乙酯及其混合物。
- 如申請專利範圍第1項之組成物，其中該丙烯酸和甲基丙烯酸之共聚物的(丙烯酸/甲基丙烯酸)單體比例在1：9至9：1範圍內。
- 如申請專利範圍第2項之組成物，其中該丙烯酸和甲基丙烯酸之共聚物的(丙烯酸/甲基丙烯酸)單體比例為約2：3。
- 如申請專利範圍第1項之組成物，其中該共聚物的分子 量在20,000至200,000範圍內。
- 如申請專利範圍第1項之組成物，其中該改質纖維素為經羧酸官能基改質的水溶性纖維素且選自羧甲基纖維素、瓊脂膠、阿拉伯膠、哥地膠(ghatti gum)、刺梧桐膠(karaya gum)、古亞膠(guar gum)、果膠、刺槐豆膠(locust bean gum)、黃蓍膠、羅望子膠(tamarind gum)、鹿角菜膠、和黃原膠、改質澱粉、海藻酸、甘露糖醛酸、葛蘿酸、和彼等的改質物、共聚物和混合物所構成的群組。
- 如申請專利範圍第5項之組成物，其中該改質纖維素為羧甲基纖維素。
- 如申請專利範圍第1項之組成物，其中該組成物不含研磨劑。
- 一種研磨半導體晶圓上之銅之方法，包括：將該晶圓與一研磨組成物接觸，該研磨組成物包括0至25重量%的氧化劑、0.05至1重量%的銅抑制劑、0.01至5重量%的銅錯合劑、0.01至5重量%的改質纖維素、0.01至5重量%的丙烯酸和甲基丙烯酸之共聚物，該改質纖維素具有羧酸官能基及界於1,000與250,000之間的分子量，及餘量的水；其中該丙烯酸和甲基丙烯酸之共聚物的(丙烯酸/甲基丙烯酸)單體比例在1：9至9：1範圍內，且該共聚物之分子量在1,000至1,000,000範圍內，其中該銅錯合劑係選自乙酸、檸檬酸、乙醇酸、乳酸、蘋果酸、草酸、水楊酸、丁二酸、酒石酸、氫硫基乙酸、甘胺酸、丙胺酸、天冬胺酸、乙 二胺、三甲基二胺、丙二酸、戊二酸、3-羥基丁酸、丙酸、酞酸、異酞酸、3-羥基水楊酸、3,5-二羥基水楊酸、五倍子酸、葡萄糖酸、焦兒茶酚、焦棓酚、鞣酸、包括彼等的鹽類和混合物、二硫代胺基甲酸二乙基酯鈉、乙醯乙醇乙酯及其混合物；以及使用一研磨墊研磨該晶圓。
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