TW201339292A - 研磨用組成物 - Google Patents
研磨用組成物 Download PDFInfo
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- TW201339292A TW201339292A TW102109302A TW102109302A TW201339292A TW 201339292 A TW201339292 A TW 201339292A TW 102109302 A TW102109302 A TW 102109302A TW 102109302 A TW102109302 A TW 102109302A TW 201339292 A TW201339292 A TW 201339292A
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- unsubstituted
- polishing
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- substituted
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- 238000005498 polishing Methods 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 12
- -1 diketone compound Chemical class 0.000 claims description 42
- 125000000524 functional group Chemical group 0.000 claims description 28
- 150000001721 carbon Chemical group 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 18
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- 239000000758 substrate Substances 0.000 claims description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
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- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
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- 101000892301 Phomopsis amygdali Geranylgeranyl diphosphate synthase Proteins 0.000 description 2
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
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- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
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- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- QMPFMODFBNEYJH-UHFFFAOYSA-N methyl 1h-1,2,4-triazole-5-carboxylate Chemical compound COC(=O)C1=NC=NN1 QMPFMODFBNEYJH-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
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- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical compound C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
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- TVQSAEOXFNDKAG-UHFFFAOYSA-N 1,1,1-trifluoro-4-phenylbutan-2-one Chemical compound FC(F)(F)C(=O)CCC1=CC=CC=C1 TVQSAEOXFNDKAG-UHFFFAOYSA-N 0.000 description 1
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- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- IQOJTGSBENZIOL-UHFFFAOYSA-N 1-(2-Furanyl)-2-propanone Chemical compound CC(=O)CC1=CC=CO1 IQOJTGSBENZIOL-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- ZOZNCAMOIPYYIK-UHFFFAOYSA-N 1-aminoethylideneazanium;acetate Chemical compound CC(N)=N.CC(O)=O ZOZNCAMOIPYYIK-UHFFFAOYSA-N 0.000 description 1
- UVBDQONHDLGQJN-UHFFFAOYSA-N 1-cyclohexyl-6-hydroxy-6-methylheptane-1,5-dione Chemical compound CC(C)(O)C(=O)CCCC(=O)C1CCCCC1 UVBDQONHDLGQJN-UHFFFAOYSA-N 0.000 description 1
- MWZDIEIXRBWPLG-UHFFFAOYSA-N 1-methyl-1,2,4-triazole Chemical compound CN1C=NC=N1 MWZDIEIXRBWPLG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
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- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
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- UFLWECJWSGWVHB-UHFFFAOYSA-N 1H-carbazole Chemical compound C1=CC=C2C3=CC=CCC3=NC2=C1 UFLWECJWSGWVHB-UHFFFAOYSA-N 0.000 description 1
- ZCBIFHNDZBSCEP-UHFFFAOYSA-N 1H-indol-5-amine Chemical compound NC1=CC=C2NC=CC2=C1 ZCBIFHNDZBSCEP-UHFFFAOYSA-N 0.000 description 1
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- ZFLFWZRPMDXJCW-UHFFFAOYSA-N 2,5-dimethyl-1h-indole Chemical compound CC1=CC=C2NC(C)=CC2=C1 ZFLFWZRPMDXJCW-UHFFFAOYSA-N 0.000 description 1
- MVHOAOSHABGEFL-UHFFFAOYSA-N 2,6-dimethyl-1h-benzimidazole Chemical compound C1=C(C)C=C2NC(C)=NC2=C1 MVHOAOSHABGEFL-UHFFFAOYSA-N 0.000 description 1
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 description 1
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- HHYPDQBCLQZKLI-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(5-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=C2N(CN(CCO)CCO)N=NC2=C1 HHYPDQBCLQZKLI-UHFFFAOYSA-N 0.000 description 1
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- RKKOMEIYHHASIN-UHFFFAOYSA-N hydroperoxyboronic acid Chemical compound OOB(O)O RKKOMEIYHHASIN-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- C23F1/30—Acidic compositions for etching other metallic material
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- C23F3/00—Brightening metals by chemical means
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- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
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- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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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
- 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
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Abstract
本發明提供一種研磨用組成物,其在研磨具有含有IV族材料之部分的研磨對象物時,可抑制因腐蝕而在研磨對象物之表面產生階差。本發明係於研磨具有含有IV族材料之部分的研磨對象物之用途中使用之研磨用組成物,且為含有氧化劑與防腐蝕劑之研磨用組成物。防腐蝕劑較好為自分子內含有之兩個以上之羰基在分子內介隔碳原子鍵結之化合物所組成群組選出之至少一種。更具體而言,較好為自1,3-二酮化合物、1,4-二酮化合物及三酮化合物所組成群組選出之至少一種。
Description
本發明係關於在研磨具有含有IV族材料之部份的研磨對象物之用途中使用之研磨用組成物。本發明又關於使用該研磨用組成物之研磨方法以及基板之製造方法。
作為減低電晶體之消耗電力或提高性能(動作特性)之技術之一已朝提高載體移動度之高移動度通道材料之檢討進展。提高該等載體之輸送特性之通道由於提高導通(ON)時之汲極電流,故獲得充分之導通電流同時降低電源電壓。該結合帶來在低電力下更高的MOSFET(金屬氧化物半導體場效電晶體)之性能。
作為高移動度通道材料而應用僅由III-V族化合物、IV族化合物、Ge(鍺)、C(碳)所成之石墨烯(graphene)等備受期待。目前,III-V族化合物通道之形成由於有提高通道之結晶性、良好地控制成長形狀之技術尚未確立之課題,因此已積極地檢討比III-V族化合物更容易導入之IV族化合物,尤其是SiGe與Ge等。
使用高移動度材料之通道可研磨具有含有IV族化合物通道、及/或Ge通道(以下亦稱為Ge材料部分)與矽
材料之部分(以下亦稱為矽材料部分)的研磨對象物而形成。此時,除了以高的研磨速度研磨Ge材料部分以外,亦要求在研磨對象物研磨後之表面上不因腐蝕而產生階差。然而,由於在研磨Ge基板之用途中過去使用之例如如特開2010-130009號公報或特表2010-519740號公報(US2011/0117740(A1))中所記載之研磨用組成物係對於Ge基板進行開發,故在研磨具有Ge材料部分與Ge材料以外的部分之研磨對象物的用途中使用時,會過度研磨及腐蝕Ge材料部分,而難以防止研磨後之表面因腐蝕產生之階差。
因此本發明之目的係提供一種在研磨具有含有如Ge之IV族材料之部分的研磨對象物時,可抑制因腐蝕而在研磨對象物之表面產生階差之研磨用組成物,且提供一種使用該研磨用組成物之研磨方法以及基板之製造方法。
為達成上述目的,本發明之第一樣態係提供一種含有氧化劑與防腐蝕劑之研磨用組成物,其係研磨具有含有IV族材料之部分的研磨對象物之用途中使用之研磨用組成物。
本發明之第二樣態係提供一種研磨方法,係使用上述第一樣態之研磨用組成物,研磨具有含有IV族材料之部分的研磨對象物。
本發明之第三樣態係提供一種製造具有含有IV族材
料之部分的基板之方法,係包含以上述第二樣態之研磨方法研磨之步驟。
以下,說明本發明之一實施形態。
本實施形態之研磨用組成物係將氧化劑與防腐蝕劑混合於水中而調製。因此,研磨用組成物含有氧化劑及防腐蝕劑。若使用具有該構成之研磨用組成物,研磨具有含有IV族材料之部分的研磨對象物,則可抑制因腐蝕而在研磨對象物之表面產生階差。
該研磨用組成物係在研磨具有含有IV族材料之部分的研磨對象物之用塗,換言之為研磨該研磨對象物製造基板之用途中使用。研磨對象物可進而具有矽材料部分。IV族材料之例列舉為Ge(鍺)、SiGe(矽鍺)等。且,矽材料之例列舉為多晶矽、氧化矽、氮化矽等。
研磨用組成物中所含之氧化劑種類並無特別限制,但以具有0.3V以上之標準電極電位較佳。使用具有0.3V以上之標準電極電位之氧化劑時,相較於使用具有未達0.3V之標準電極電位之氧化劑時,就提高以研磨用組成物進行之含有IV族材料之部分的研磨速度方面有利。具有0.3V以上之標準電極電位之氧化劑的具體例列舉為例如過氧化氫、過氧化鈉、過氧化鋇、有機氧化劑、臭氧水
、銀(II)鹽、鐵(III)鹽、及過錳酸、鉻酸、重鉻酸、過氧二硫酸、過氧磷酸、過氧硫酸、過氧硼酸、過甲酸、過乙酸、過苯甲酸、過苯二甲酸、次氯酸(hypochlorous acid)、次溴酸、次碘酸、氯酸、亞氯酸、過氯酸、溴酸、碘酸、過碘酸、硫酸、過硫酸、檸檬酸、二氯異氰尿酸及該等之鹽等。該等中,就大幅提高以研磨用組成物進行之含有IV族材料之部分的研磨速度而言,最好為過氧化氫、過硫酸銨、次氯酸、次氯酸鈉、過碘酸及二氯異氰尿酸鈉。
又,所謂標準電極電位為參與氧化反應之所有化學種處於標準狀態時以下述數式1表示。
[數1]E0=-△G0/nF=(RT/nF)lnK...數式1
此處,E0為標準電極電位,△G0為氧化反應之標準吉布斯能(Gibbs energy)變化,K為其平行常數,F為法拉第常數,T為絕對溫度,n為參與氧化反應之電子數。由上述數式1可了解,標準電極電位隨溫度而變化,故本說明書中採用在25℃之標準電極電位。又,水溶液系之標準電極電位係記載於例如修訂4版化學便覽(基礎編)II,pp464-468(日本化學會編)等中。
研磨用組成物中之氧化劑含量較好為0.00001mol/L以上,更好為0.001mol/L以上。隨著氧化劑之含量變多而提高以研磨用組成物進行之含有IV族材料之部分的研磨速度。
研磨用組成物中之氧化劑含量又較好為100mol/L以下,更好為50mol/L以下,進而更好為10mol/L以下,最好為1mol/L以下。隨著氧化劑之含量變少,除可壓抑研磨用組成物之材料成本以外,也可減輕研磨使用後之研磨用組成物之處理,亦即廢液處理之負荷。
研磨用組成物中所含防腐蝕劑之種類並無特別限制,但較好為由分子內含有之兩個以上之羰基介隔碳原子鍵結之化合物所組成群組選出之至少一種。過去之研磨用組成物因研磨用組成物中之添加劑(尤其是錯化劑)等而引起含有IV族材料之部分的過度腐蝕。相對於此,尤其是使用分子內含有之兩個以上之羰基介隔碳原子鍵結之化合物作為防腐蝕劑之本實施形態之研磨用組成物的情況,認為IV族材料會與防腐蝕劑之分子內的兩個以上之羰基鍵結而形成不溶性錯合物,且形成不溶性之脆性膜。其結果,認為可抑制因過去之研磨用組成物中之添加劑(尤其是錯化劑)等對IV族材料之過度腐蝕,且可抑制因腐蝕而在研磨對象物表面上產生階差。又,上述機制係推測者,本實施形態並不受上述機制之任何限制。
分子內含有之兩個以上之羧基在分子內介隔碳原子鍵結之化合物之例列舉為例如以下述通式(1)表示之二酮化合物。
(但,通式(1)中,R1為碳數1~4之直鏈狀或分支狀之伸烷基,R2及R3各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀烷基、羥基甲基、羥基乙基、或無取代或具有取代基之碳數6~20之芳基,X1及X2各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、無取代或具有取代基之碳數6~20之芳基、下述官能基(1)或下述官能基(2),此時,X1與R2、R2與R3、及R3與X2之一組以上可直接或介隔碳原子相互鍵結而形成環狀構造),
(但,官能基(1)中之R4及R5,及官能基(2)中之R6各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、或無取代或具有取代基之芳基)。
更具體而言,較好地列舉由前述通式(1)中之R1為碳數為2以下之以下述通式(2)表示之1,3-二酮化合物、及以下述通式(3)表示之1,4-二酮化合物所組成群組選出之至少一種化合物。
(但,通式(2)及通式(3)中,R7、R8、R9、
R10、R11及R12各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、或無取代或具有取代基之碳數6~20之芳基,X1及X2各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、無取代或具有取代基之碳數6~20之芳基、下述官能基(1)或下述官能基(2),此時,R9與X1、R9與R10、R11與R12、及R12與X2之一組以上亦可直接或介隔碳原子相互鍵結而形成環狀構造),
(但,官能基(1)中之R4及R5,及官能基(2)中之R6各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、或無取代或具有取代基之碳數6~20之芳基)。
研磨用組成物中所含之防腐蝕劑,作為在分子內含有
之兩個以上之羰基介隔碳原子鍵結之化合物中,以前述通式(2)表示之1,3-二酮化合物之例,具體而言列舉為β-二酮化合物、β-酮醯胺化合物及β-酮酯化合物等。更具體而言列舉為例如乙醯基丙酮、3-甲基-2,4-戊二酮、3-乙基-2,4-戊二酮、3,5-庚二酮、6-甲基-2,4-庚二酮、2,6-二甲基-3,5-庚二酮、2,2,6,6-四甲基庚-3,5-二酮、2-乙醯基環戊酮、3-氯乙醯基丙酮、三氟乙醯基丙酮、2,4-己二酮、苯甲醯基丙酮、苯甲基醯三氟丙酮、二苯甲醯基甲烷、N,N-二甲基乙醯基乙醯胺、N,N-二乙基乙醯基乙醯胺、N,N-二甲基-2-氯乙醯基乙醯胺、1,3-二乙氧基丙-1,3-二酮、N,N-二甲基-4-氧代戊醯胺、5-氧代己酸甲酯、二乙醯基乙酸乙酯、N-甲基乙醯乙酸醯胺、N,N-二甲基乙醯乙酸醯胺、N-(2-羥基乙基)乙醯乙酸醯胺、乙醯乙酸醯替苯胺、N-(2-甲基苯基)乙醯乙酸醯胺、N-(4-甲氧基苯基)乙醯乙酸醯胺、N-(4-氯苯基)乙醯乙酸醯胺、3-氧代戊酸醯胺、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油酯、乙醯乙酸月桂酯、乙醯乙酸硬脂酯、乙醯乙酸油酯、乙醯乙酸苄酯、3-氧代戊酸甲酯、3-氧代戊酸辛酯等。
又,研磨用組成物中所含防腐蝕劑為分子內含有的兩個以上之羰基介隔碳原子鍵結之化合物中,以前述通式(3)表示之1,4-二酮化合物之例,具體而言列舉為γ-二酮化合物等。更具體而言列舉為例如呋喃甲醯基丙酮、丙酮醯基丙酮(acetonyl acetone)、苯乙基丙酮、2,5-己二
酮、1,4-二苯基-1,4-丁二酮、1-苯基-1,4-戊二酮、1,5-二苯基-1,4-戊二酮、1,4-雙(4-甲基苯基)-1,4-丁二酮、1,4-雙(4-甲氧基苯基)-1,4-丁二酮、1,4-雙(4-氯苯基)-1,4-丁二酮等。
又,以上述通式(2)及(3)表示之二酮化合物以外之以上述通式(1)表示之二酮化合物,列舉為例如2,6-庚二酮、2,7-辛二酮、3-甲基-3-異丙基-2,6-庚二酮、3-乙醯基庚-2,6-二酮、3-亞甲基-2,6-庚二酮、1-苯基-1,5-庚二酮、1-苯基-3,6,6-三甲基-1,5-庚二酮、1-環己基-6-羥基-6-甲基-1,5-庚二酮等。
該等中,較好為由前述通式(1)~(3)中之X1及X2之至少一個為由具有4個以上之碳原子之無取代或具有取代基之直鏈狀、分支狀、或環狀之烷基、羥基甲基或羥基乙基之二酮化合物所組成群組選出之至少一種,進而,更好為由前述通式(1)~(3)中之R2~R12各獨立為氫原子或鹵原子之二酮化合物所組成群組選出之至少一種。該等可單獨使用,亦可組合兩種以上使用。
又,分子內含有之兩個羰基介隔碳原子鍵結之化合物之其他例,亦較好舉例由下述通式(4)表示之三酮化合物。
(但,通式(4)中,R13及R14各獨立為碳數1~4之直鏈狀或分支狀之伸烷基,R15、R16、R17及R18各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、或無取代或具有取代基之碳數6~20之芳基,X1及X2各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、無取代或具有取代基之碳數6~20之芳基、下述官能基(1)或下述官能基(2),此時,X1與R15、R15與R16、R16與R17、R17與R18、及R18與X2之一組以上亦可直接或介隔碳原子相互鍵結而形成環狀構造),
(但,官能基(1)中之R4及R5,及官能基(2)中之R6各獨立為氫原子、鹵原子、無取代或具有取代基之碳數1~10之直鏈狀、分支狀或環狀之烷基、羥基甲基、羥基乙基、或無取代或具有取代基之碳數6~20之芳基)。
以上述通式(4)表示之三酮化合物之更具體之例列舉為例如2,4,6-庚三酮、2,4,7-辛三酮等。
又,上述通式(1)~(4)及官能基(1)~(2)中於R2~R12、R15~R18、及X1~X2所用之鹵原子之例列舉為氟原子、氯原子、溴原子、碘原子等。
上述通式(1)~(4)及官能基(1)~(2)中於R2~R12、R15~R18、及X1~X2所用之烷基或芳基亦可具有取代基。該取代基之例列舉為例如烷基、芳基、芳烷基、烷氧基、芳氧基、鹵原子(Cl、Br、F)、烷氧基羰基、烷硫基、芳硫基、胺基、經取代之胺基、醯胺基、磺醯胺基、脲基、經取代之脲基、胺甲醯基、經取代之胺甲醯基、胺磺醯基、經取代之胺磺醯基、烷基磺醯基、芳基磺醯基、羥基、氰基、硝基、磺基、羧基等。又,視情況存在之取代基不與經取代之上述通式(1)~(4)及官能基(1)~(2)中之R2~R12、R15~R18、及X1~X2相同。例
如,R2~R12、R15~R18、及X1~X2為烷基時,並不再以烷基取代。
研磨用組成物中之防腐蝕劑為分子內含有之兩個以上之羰基在分子內介隔碳原子鍵結之化合物時,其含量上限較好為10重量%以下,更好為8重量%以下,又更好為5重量%以下。隨著分子內含有之兩個以上之羰基介隔碳原子鍵結之化合物之含量變少,研磨速度提高故較佳。
研磨用組成物中之防腐蝕劑為分子內含有之兩個以上之羰基在分子內介隔碳原子鍵結之化合物時,其含量之下限較好為0.0001重量%以上,更好為0.001重量%以上,又更好為0.005重量%以上。隨著分子內含有之兩個以上之羰基在分子內介隔碳原子鍵結之化合物含量變多,而抑制腐蝕。其結果,可抑制因腐蝕造成之階差發生故較佳。
依據本實施形態可獲得以下之作用效果。
本實施形態之研磨用組成物中為了抑制因腐蝕而在研磨對象物之表面產生之階差,而使用與研磨對象物之含有IV族材料之部分相互作用之防腐蝕劑。因此,該研磨組成物適用在研磨具有含有IV族材料之部分的研磨對象物之用途中。
前述實施形態亦可如下述般變更。
.前述實施形態之研磨用組成物可含有兩種以上之氧化劑。
.前述實施形態之研磨用組成物可含有兩種以上之防腐蝕劑。例如,可組合使用分子內含有之兩個以上之羰基
在分子內介隔碳原子鍵結之化合物與作為其以外之其他防腐蝕劑之含氮化合物。又,含氮化合物之例列舉為胺化合物或含氮雜環化合物等,但以含氮雜環化合物較佳。含氮雜環化合物之具體例包含吡咯、吡唑、咪唑、三唑、四唑、吡啶、吡嗪、嗒嗪、吡啶、吲哚嗪、吲哚、異吲哚、吲唑、嘌呤、喹嗪(quinolizine)、喹啉、異喹啉、萘啶、酞嗪、喹喔啉、喹唑啉、噌啉、蝶啶、噻唑、異噻唑、噁唑、異噁唑、呋咱等。吡唑之例列舉為1H-吡唑、4-硝基-3-吡唑羧酸、3,5-吡唑羧酸、3-胺基-5-苯基吡唑、5-胺基-3-苯基吡唑、3,4,5-三溴吡唑、3-胺基吡唑、3,5-二甲基吡唑、3,5-二甲基-1-羥基甲基吡唑、3-甲基吡唑、1-甲基吡唑、3-胺基-5-甲基吡唑、4-胺基-吡唑并[3,4-d]嘧啶、別嘌呤醇(allopurinol)、4-氯-1H-吡唑并[3,4-D]嘧啶、3,4-二羥基-6-甲基吡唑并(3,4-B)-吡啶、6-甲基-1H-吡唑并[3,4-b]吡啶-3-胺等。咪唑之例包含咪唑、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基吡唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、2-胺基苯并咪唑、2-氯苯并咪唑、2-甲基苯并咪唑、2-(1-羥基乙基)苯并咪唑、2-羥基苯并咪唑、2-苯基苯并咪唑、2,5-二甲基苯并咪唑、5-甲基苯并咪唑、5-硝基苯并咪唑、1H-嘌呤等。三唑之例包含1,2,3-三唑、1,2,4-三唑、1-甲基-1,2,4-三唑、甲基-1H-1,2,4-三唑-3-羧酸酯、1,2,4-三唑-3-羧酸、1,2,4-三唑-3-羧酸甲酯、1H-1,2,4-三唑-3-硫醇、3,5-二胺基-1H-1,2,4-三唑、3-胺基-
1,2,4-三唑-5-硫醇、3-胺基-1H-1,2,4-三唑、3-胺基-5-苄基-4H-1,2,4-三唑、3-胺基-5-甲基-4H-1,2,4-三唑、3-硝基-1,2,4-三唑、3-溴-5-硝基-1,2,4-三唑、4-(1,2,4-三唑-1-基)酚、4-胺基-1,2,4-三唑、4-胺基-3,5-二丙基-4H-1,2,4-三唑、4-胺基-3,5-二甲基-4H-1,2,4-三唑、4-胺基-3,5-二庚基-4H-1,2,4-三唑、5-甲基-1,2,4-三唑-3,4-二胺、1H-苯并三唑、1-羥基苯并三唑、1-胺基苯并三唑、1-羧基苯并三唑、5-氯-1H-苯并三唑、5-硝基-1H-苯并三唑、5-羧基-1H-苯并三唑、5-甲基-1H-苯并三唑、5,6-二甲基-1H-苯并三唑、1-(1’,2’-二羧基乙基)苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]苯并三唑、1-[N,N-雙(羥基乙基)胺基甲基]-5-甲基苯并三唑等。四唑之例包含1H-四唑、5-甲基四唑、5-胺基四唑、5-苯基四唑等。吲唑之例包含1H-吲唑、5-胺基-1H-吲唑、5-硝基-1H-吲唑、5-羥基-1H-吲唑、6-胺基-1H-吲唑、6-硝基-1H-吲唑、6-羥基-1H-吲唑、3-羧基-5-甲基-1H-吲唑等。吲哚之例包含1H-吲哚、1-甲基-1H-吲哚、2-甲基-1H-吲哚、3-甲基-1H-吲哚、4-甲基-1H-吲哚、5-甲基-1H-吲哚、6-甲基-1H-吲哚、7-甲基-1H-吲哚、4-胺基-1H-吲哚、5-胺基-1H-吲哚、6-胺基-1H-吲哚、7-胺基-1H-吲哚、4-羥基-1H-吲哚、5-羥基-1H-吲哚、6-羥基-1H-吲哚、7-羥基-1H-吲哚、4-甲氧基-1H-吲哚、5-甲氧基-1H-吲哚、6-甲氧基-1H-吲哚、7-甲氧基-1H-吲哚、4-氯-1H-吲哚、5-氯-1H-吲哚、6-氯-1H-吲哚、7-氯-1H-吲哚、4-羧基-1H-吲哚、5-羧基-1H-吲哚、6-羧
基-1H-吲哚、7-羧基-1H-吲哚、4-硝基-1H-吲哚、5-硝基-1H-吲哚、6-硝基-1H-吲哚、7-硝基-1H-吲哚、4-硝醯基-1H-吲哚、5-硝醯基-1H-吲哚、6-硝醯基-1H-吲哚、7-硝醯基-1H-吲哚、2,5-二甲基-1H-吲哚、1,2-二甲基-1H-吲哚、1,3-二甲基-1H-吲哚、2,3-二甲基-1H-吲哚、5-胺基-2,3-二甲基-1H-吲哚、7-乙基-1H-吲哚、5-(胺基甲基)吲哚、2-甲基-5-胺基-1H-吲哚、3-羥基甲基-1H-吲哚、6-異丙基-1H-吲哚、5-氯-2-甲基-1H-吲哚等。其中較好為1H-1,2,4-三唑,或苯并三唑。
.前述實施形態之研磨用組成物亦可進一步含有研磨粒。研磨粒可為無機粒子及有機粒子之任一種。無機粒子之具體例列舉為由二氧化矽、氧化鋁、氧化鈰、氧化鈦等金屬氧化物所成之粒子。有機粒子之具體例列舉為聚甲基丙烯酸甲酯粒子。其中以二氧化矽粒子較佳,最好為膠體二氧化矽。
研磨粒亦可經表面修飾。通常之膠體二氧化矽由於在酸性條件下Zeta電位之值接近於零,故在酸性條件下二氧化矽粒子彼此不會電性排斥而容易引起凝聚。相對於此,即使經表面修飾以使在酸性條件下具有Zeta電位較大之正或負值之研磨粒在酸性條件下亦彼此為強的排斥而獲得良好之分散,結果提高研磨用組成物之保存安定性。此種表面修飾研磨顆粒可藉由例如混合鋁、鈦或鋯等之金屬或該等之氧化物與研磨粒而摻雜於研磨粒表面獲得。
或者,研磨用組成物中之表面修飾研磨粒亦可為固定
化有有機酸之二氧化矽。其中以固定化有有機酸之膠體二氧化矽較佳。有機酸對膠體二氧化矽之固定化係藉由將有機酸之官能基化學鍵結於膠體二氧化矽表面而進行。僅僅使膠體二氧化矽與有機酸共存並無法發揮有機酸對膠體二氧化矽之固定化。若將有機酸之一種的磺酸固定化於膠體二氧化矽上,則可藉例如“經硫醇基之定量氧化之磺酸官能基化二氧化矽(Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups)”,Chem.Commun.246-247(2003)所記載之方法進行。具體而言,可藉由使3-巰基丙基三甲氧基矽烷等之具有硫醇基之矽烷偶合劑偶合於膠體二氧化矽上後以過氧化氫使硫醇基氧化,獲得磺酸固定化於表面之膠體二氧化矽。或者,若將磺酸固定化於膠體二氧化矽,則可藉例如“用於將羧基導入於二氧化矽凝膠表面之含光可反應之2-硝基苄酯之新穎矽烷偶合劑(Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel)”,Chemistry Letters,3,228-229(2000)所記載之方法進行。具體而言,將含光反應性2-硝基苄基酯之矽烷偶合劑偶合於膠體二氧化矽上之後藉由光照射,可獲得羧酸固定化於表面之膠體二氧化矽。
研磨用組成物中之研磨粒含量較好為0.1質量%以上,更好為0.5質量%以上,又更好為1質量%以上。隨著研磨粒含量變多,而提高以研磨用組成物進行之對於具
有含有IV族材料之部分的研磨對象物之研磨速度。
研磨用組成物中之研磨粒含量較好為20質量%以下,更好為15質量%以下,又更好為10質量%以下。隨著研磨粒含量變少,除可壓抑研磨用組成物之材料成本以外,亦不易引起研磨粒之凝聚。且,藉由使用研磨用組成物研磨具有含有IV族材料之部分的研磨對象物而容易獲得刮痕少之研磨面。
.前述實施形態之研磨用組成物亦可含水作為分散或溶解各成分用之分散介質或溶劑。就抑制阻礙其他成分之作用的觀點而言,較好為儘可能不含雜質之水,具體而言,較好為以離子交換樹脂去除雜質離子後,通過過濾器去除異物之純水或超純水,或蒸餾水。
.前述實施形態之研磨用組成物亦可藉酸或鹼進行pH調整。pH之下限並無特別限制,但較好為3以上,更好為5以上,又更好為6以上。pH較高時有可抑制腐蝕率同時可獲得高的研磨速度之優點。又,pH之上限並無特別限制,但較好為12以下,更好為11以下,又更好為10以下。pH太高時,會有膠體二氧化矽等研磨粒溶解之虞。因此,pH若較低可抑制膠體二氧化矽等研磨粒之溶解。其結果,有提高漿液之儲存安定性之優點。至於pH調整劑可使用習知之有機酸、有機鹼、無機酸、無機鹼或該等之鹽。
.前述實施形態之研磨用組成物亦可視需要含如防腐劑之習知添加劑。
.前述實施形態之研磨用組成物可為單液型,亦可為以二液型為代表之多液型。
.前述實施形態之研磨用組成物亦可藉由以水稀釋研磨用組成物之原液而調製。
如上述,本發明之研磨用組成物適用於具有含有IV族材料之部分的研磨對象物之研磨。因此,本發明提供以本發明之研磨用組成物研磨具有含有IV族材料之部分的研磨對象物之研磨方法。且,本發明提供包含以前述研磨方法研磨具有含有IV族材料之部分的研磨對象物之步驟的基板製造方法。
至於研磨裝置可使用安裝有保持具有研磨對象物之基板等之載具及可改變轉數之馬達等,且具有可貼附研磨墊(研磨布)之研磨壓盤之一般研磨裝置。
前述研磨墊可無特別限制地使用一般不織布、聚胺基甲酸酯、及多孔質氟樹脂等。研磨墊較好施以溝槽加工以使研磨液聚集。
研磨條件並無特別限制,例如,研磨壓盤之轉數較好為10~500 rpm,施加於具有研磨對象物的基板之壓力(研磨壓力)較好為0.5~10 psi。將研磨用組成物供給於研磨墊之方法亦無特別限制,可採用例如藉泵等之連續供給方法。其供給量並無限制,較好總是以本發明之研磨用組成物覆蓋研磨墊表面。
研磨結束後,在流水中洗淨基板,以旋轉乾燥機等甩落附著於基板上之水滴並經乾燥,藉此獲得具有含有IV族材料之部分的基板。
接著,說明本發明之實施例及比較例。
藉由使氧化劑及防腐蝕劑與水混合,調製實施例1~60及比較例1~6之研磨用組成物。表1~3之“防腐蝕劑”欄之“種類”欄中列出各研磨用組成物中所含防腐蝕劑之種類。又,“含量(mol/L)”及“含量(重量%)”欄中列出各研磨用組成物中之該防腐蝕劑或其以外之添加劑含量。又關於“含量(重量%)”,係以研磨用組成物之比重作為1計算。同欄中,“-”之標記係表示不含該防腐蝕劑或其以外之添加劑。表1~3之“pH”欄中表示各研磨用組成物之pH。又,表1~3中雖未顯示,但各研磨用組成物中均含1.0重量%之膠體二氧化矽(平均二次粒徑約60nm,平均一次粒徑約30nm)作為研磨粒。且,各研磨用組成物中係以使成為0.1重量%(約0.0134mol/L,以研磨用組成物之比重作為1計算)之方式添加次氯酸鈉作為氧化劑,pH係藉添加無機酸或無機鹼調整至特定值。
將鍺空白晶圓切割成2cm見方之大小的晶圓小片,在25℃浸漬於實施例1~60及比較例1~6之各研磨用組成物中5分鐘。由浸漬前後之晶圓小片之重量差與鍺之比重(6.2g/cm3)換算之鍺之腐蝕速度示於表1~3之“評價1”
欄中之“Ge之溶解速度”欄中。且,以表4所示條件研磨鍺空白晶圓。針對以表4所示之條件研磨一定時間時之研磨速度,係由以直流4探針法進行之薄片電阻之測定求得之研磨前後之空白晶圓厚度差除以研磨時間而求得。其結果示於表1~3之“評價1”欄之“Ge之研磨速度”欄中。
同樣地,將矽鍺空白晶圓切割成2cm見方之大小的晶圓小片,在25℃浸漬於實施例1~60及比較例1~6之各研磨用組成物中5分鐘。由浸漬前後之晶圓小片之重量差與矽鍺之比重(4.1g/cm3)換算之矽鍺之腐蝕速度示於表1~3之“評價2”欄的“SiGe之腐蝕速度”欄中。且,以表4所示條件研磨矽鍺空白晶圓。關於以表4所示之條件研磨一定時間時之研磨速度,係由以直流4探針法進行之薄片電阻之測定求得之研磨前後之空白晶圓厚度差除以研磨時間而求得。其結果示於表1~3之“評價2”欄之“SiGe之研磨速度”欄中。
如表1~3所示,使用實施例1~60之研磨用組成物時,相較於未滿足本發明要件之比較例1~6時,認為可發揮關於腐蝕抑制之顯著優異效果。由該結果,暗示本發明之研磨用組成物對於用以抑制因腐蝕造成之階差產生為有效。
又,本申請案係基於2012年3月16日申請之日本專利申請案第2012-061156號,其揭示內容以全文加以援用供參考。
Claims (10)
- 一種研磨用組成物,其係研磨具有含有IV族材料之部分的研磨對象物之用途中使用之研磨用組成物,且含有氧化劑與防腐蝕劑。
- 如請求項1之研磨用組成物,其中前述防腐蝕劑係自分子內含有之兩個以上之羰基在分子內介隔碳原子鍵結之化合物所組成群組選出之至少一種。
- 如請求項2之研磨用組成物,其中前述化合物係以下述通式(1)表示之二酮化合物,
- 如請求項3之研磨用組成物,其中前述化合物係自通式(1)中之R1的碳原子數為2以下之以下述通式(2)表示之二酮化合物及以下述通式(3)表示之二酮化合物所組成群組選出之至少一種,
- 如請求項3或4之研磨用組成物,其中前述化合物係自前述通式(1)~(3)中之X1及X2之至少一個為具有4個以上之碳原子之無取代或具有取代基之直鏈狀、分支狀或環狀之烷基、羥基甲基或羥基乙基之二酮化合物所組成群組選出至少一種。
- 如請求項3~5中任一項之研磨用組成物,其中前述化合物係自前述通式(1)~(3)中之R2~R12各獨立為氫原子或鹵原子之二酮化合物所組成群組選出之至少一種。
- 如請求項2之研磨用組成物,其中前述化合物係以下述通式(4)表示之化合物:
- 如請求項1~7中任一項之研磨用組成物,其pH為5以上12以下。
- 一種研磨方法,其係使用如請求項1~8中任一項之研磨用組成物研磨具有含有IV族材料之部分的研磨對象物。
- 一種具有含有IV族材料之部分的基板之製造方法,其包含以如請求項9之研磨方法進行研磨之步驟。
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JPWO2013137192A1 (ja) | 2015-08-03 |
US9376594B2 (en) | 2016-06-28 |
KR20140129175A (ko) | 2014-11-06 |
US20150069016A1 (en) | 2015-03-12 |
JP6084965B2 (ja) | 2017-02-22 |
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KR102022139B1 (ko) | 2019-09-17 |
TWI550078B (zh) | 2016-09-21 |
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