TWI805556B - 表面處理組合物 - Google Patents
表面處理組合物 Download PDFInfo
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- TWI805556B TWI805556B TW106128239A TW106128239A TWI805556B TW I805556 B TWI805556 B TW I805556B TW 106128239 A TW106128239 A TW 106128239A TW 106128239 A TW106128239 A TW 106128239A TW I805556 B TWI805556 B TW I805556B
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- Taiwan
- Prior art keywords
- surface treatment
- treatment composition
- silicon
- soluble polymer
- group
- Prior art date
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 125000000129 anionic group Chemical group 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- -1 poly(N-vinylformamide) Polymers 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002612 dispersion medium Substances 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 2
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- 230000007547 defect Effects 0.000 abstract description 26
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- 229920005591 polysilicon Polymers 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
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- 239000010703 silicon Substances 0.000 description 7
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- 239000002585 base Substances 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
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- 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 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明係提供一種藉由充分除去含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷,便可對研磨畢研磨對象物之表面施行處理的表面處理組合物。
本發明的表面處理組合物,係使用於含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物之表面處理,且pH未滿9.0,含有:具有僅由碳原子構成、或由碳原子與氮原子所構成主鏈的非離子水溶性高分子(A);以及具有主鏈與側鏈的陰離子水溶性高分子(B);而,該主鏈係僅由碳原子構成;該側鏈係鍵結於該僅由碳原子構成的主鏈,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基。
Description
本發明係關於表面處理組合物。
近年,隨半導體基板表面的多層配線化,在製造裝置時,對半導體基板施行物理性研磨而平坦化,即利用所謂的「化學性機械研磨(Chemical Mechanical Polishing;CMP)」技術。CMP係使用含有二氧化矽、氧化鋁、氧化鈰等磨粒、防蝕劑、界面活性劑等的研磨用組合物(漿料),對半導體基板等研磨對象物(被研磨物)的表面施行平坦化的方法,研磨對象物(被研磨物)係例如:矽、多晶矽、氧化矽、氮化矽、由金屬等構成的配線、插塞等。
經CMP步驟後的半導體基板表面上會殘留雜質(缺陷)。雜質係包括有:源自CMP所使用研磨用組合物的磨粒、金屬;防蝕劑、界面活性劑等有機物;研磨對象物之含矽材料;因對金屬配線、插塞等施行研磨而生成的含矽材料、金屬;以及由各種墊等產生的墊屑等有機物等等。
若半導體基板表面因該等雜質而遭污染,便會對半導體的電特性造成不良影響,會有降低裝置可靠度的可能性。所以,最好從經CMP步驟後的被研磨過之研磨對象物(研磨畢研磨對象物)表面上,除去該等雜質。
供除去該等雜質用的洗淨用組合物,已知有例如專利文獻1~4所揭示。
先前技術文獻
專利文獻
專利文獻1:日本專利特開2009-147389號公報
專利文獻2:日本專利特開2001-064679號公報
專利文獻3:日本專利特開2006-005246號公報
專利文獻4:日本專利特開2005-303060號公報
然而,習知技術會有無法將具有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物中所殘存的缺陷充分除去之問題。
所以,本發明所欲解決的課題在於提供:藉由充分除去含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷,便可對研磨畢研磨對象物的表面施行處理的表面處理組合物。
本發明者鑑於上述課題進行深入鑽研。結果發現藉由提供下述表面處理組合物便可解決上述課題,遂完成本發明課題。該表面處理組合物係使用於含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物之表面處理,且pH未滿9.0,含有:具有僅由碳原子構成、或由碳原子與氮原子所構成主鏈的非離子水溶性高分子(A)(亦稱「非離子水溶性高分子(A)」);以及具有主 鏈與側鏈的陰離子水溶性高分子(B)(亦稱「陰離子水溶性高分子(B)」);而,該主鏈係僅由碳原子構成;該側鏈係鍵結於該僅由碳原子構成的主鏈,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基。
根據本發明,可提供藉由充分除去具有含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷,便可對研磨畢研磨對象物的表面施行處理的表面處理組合物。
本發明的表面處理組合物係使用於含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物之表面處理,且pH未滿9.0,含有:具有僅由碳原子構成、或由碳原子與氮原子所構成主鏈的非離子水溶性高分子(A);以及具有主鏈與側鏈的陰離子水溶性高分子(B);而,該主鏈係僅由碳原子構成;該側鏈係鍵結於該僅由碳原子構成的主鏈,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基。
藉由該構成而充分除去具有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷,便可對研磨畢研磨對象物的表面施行處理。
另外,本發明的組合物係除去研磨畢研磨對象物(基板)上殘留的雜質(缺陷),就此觀點而言,可謂使該研磨畢研磨對象物(基板)表面的表面狀態變化(處理)。所以,該組合 物稱「表面處理組合物」。
(CMP步驟)
依如上述,本發明的表面處理組合物係使用於CMP步驟後。
此處,CMP步驟係可為由單一步驟構成的研磨步驟、亦可為由複數步驟構成的研磨步驟。由複數步驟構成的研磨步驟係可例如:在預研磨步驟(粗研磨步驟)後施行精拋光(finishing)研磨步驟的步驟;或者經1次研磨步驟後再施行1次或2次以上的2次研磨步驟,然後施行精拋光研磨步驟的步驟。又,CMP步驟所使用的研磨用組合物係供對具有矽-矽鍵與氮-矽鍵的研磨對象物施行適當研磨,可適當使用習知的研磨用組合物,較佳係可使用例如膠體二氧化矽(colloidal silica)等磨粒、含有PVP等水溶性高分子者等。又,研磨裝置亦可使用一般的研磨裝置,可使用單面研磨裝置或雙面研磨裝置中之任一者。研磨墊最好使用聚氨酯等。
依此,藉由對研磨對象物施行CMP步驟,便製得研磨畢研磨對象物。
(研磨畢研磨對象物)
被施行CMP步驟之對象的「研磨對象物」係含有矽-矽鍵與氮-矽鍵。所以,被施行CMP步驟的「研磨畢研磨對象物」亦含有矽-矽鍵、與氮-矽鍵。又,藉由除去殘留的雜質而施行表面處理的「表面處理對象物」亦含有矽-矽鍵與氮-矽鍵。
此處,具有矽-矽鍵的研磨對象物(研磨畢研磨對象物)係可例如:多晶矽、非晶矽、單晶矽、n型摻雜單晶矽、p 型摻雜單晶矽、SiGe等Si系合金等等。具有矽-氮鍵的研磨對象物(研磨畢研磨對象物)係可例如氮化矽膜、SiCN(氮碳化矽)等。
進一步補充,所謂「含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物」係研磨畢研磨對象物,在該研磨畢研磨對象物中,某區域含有「矽-矽鍵」,而其他區域則含有「氮-矽鍵」。
根據本發明的表面處理組合物,可獲得習知無法達成之將含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷充分除去。
(表面處理組合物)
(非離子水溶性高分子(A))
本發明的表面處理組合物係含有具有僅由碳原子構成、或者由碳原子與氮原子所構成主鏈的非離子水溶性高分子(A)。此處所謂「主鏈」係指構成高分子的鏈式化合物之主要鏈。本發明非離子水溶性高分子(A)的主鏈係僅由碳原子構成,或由碳原子與氮原子構成。根據該實施形態,能有效率地達成本發明所所期待效果。
所示,上述構成單元係含有-J及-E中之至少一者。
此種表面處理組合物達成本發明所期待效果的機制,推測如下。當然,本發明的保護範圍並不因該機制而受限制。即,含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物,因為一般在表面存在氫原子,因而水的接觸角高。相對於此,藉由使用本實施形態的非離子水溶性高分子(A),該非離子水溶性高分子(A)發揮潤濕劑的作用,降低研磨畢研磨對象物表面的水接觸角。推測依此輕易除去雜質。另外,本說明書中,*係表 示鍵結位置。
所示,R1~R4中至少一者係-J,-J較佳係羥基。
所示。
所示。
其中,就從達本發明所期待效果的觀點,較佳係本形態的(1)及本形態的(2),更佳係本形態的(1)。
本發明較佳實施形態中,上述非離子水溶性高分子(A)係從由:聚乙烯醇(PVA)、構造之其中一部分含有源自聚乙烯醇(PVA)之構成單元的共聚物、聚乙烯吡咯烷酮(polyvinylpyrrolidone;PVP)、構造之其中一部分含有源自聚乙烯吡咯烷酮(PVP)之構成單元的共聚物、聚乙烯己內醯胺、構造之其中一部分含有源自聚乙烯己內醯胺之構成單元的共聚物、聚N-乙烯基甲醯胺、及構造之其中一部分含有源自聚N-乙烯基甲醯胺之構成單元的共聚物所構成群組中選擇至少1種。根據該實施形態,可有效率地達成本發明所期待的效果。
另外,當上述非離子水溶性高分子(A)係共聚物的情況,其形態係可為嵌段共聚物、無規共聚物、接枝共聚物、交替共聚物中之任一者。
本發明較佳實施形態中,上述非離子水溶性高分子(A)較佳係聚乙烯醇(PVA)、構造之其中一部分含有源自聚乙烯醇(PVA)之構成單元的共聚物、聚乙烯吡咯烷酮(PVP)、或構造之其中一部分含有源自聚乙烯吡咯烷酮(PVP)之構成單元的共聚物,更佳上述非離子水溶性高分子(A)係聚乙烯醇(PVA)、 或構造之其中一部分含有源自聚乙烯醇(PVA)之構成單元的共聚物。藉由該實施形態,可有效地達成本發明所期待效果。
再者,本發明較佳實施形態中,上述聚乙烯醇(PVA)或構造之其中一部分含有源自上述聚乙烯醇(PVA)之構成單元的共聚物,皂化度為60%以上。藉由該實施形態便可有效地達成本發明所期待效果。又,本發明較佳實施形態中,皂化度較佳係80%以上、更佳係90%以上。
本發明中,非離子水溶性高分子(A)的重量平均分子量,就從充分除去缺陷的觀點,較佳係800以上、更佳係2,000以上、特佳係4,000以上、最佳係6,000以上、最最佳係8,000以上。又,就從充分除去缺陷的觀點,較佳係80,000以下、更佳係60,000以下、特佳係45,000以下、最佳係30,000以下、最最佳係20,000以下。另外,重量平均分子量係利用凝膠滲透色層分析儀(GPC),以已知分子量的聚苯乙烯為基準物質進行測定。
非離子水溶性高分子(A)的含有量,就從充分除去缺陷的觀點,相對於表面處理組合物的總質量,較佳係0.01質量%以上、更佳係0.05質量%以上、特佳係0.08質量%以上。又,較佳係5質量%以下、更佳係1質量%以下、特佳係0.6質量%以下、最佳係0.3質量%以下、最最佳係0.2質量%以下。
(陰離子水溶性高分子(B))
本發明的表面處理組合物係含有陰離子水溶性高分子(B),而上述陰離子水溶性高分子(B)係含有僅由碳原子構成的主鏈、與側鏈,該側鏈係鍵結於僅由上述碳原子構成的主鏈上,且具有磺酸基或其鹽的基、或者具有羧基或其鹽的基。此種表 面處理組合物達成本發明所期待效果的機制,推測如下。當然,本發明保護範圍並不因該機制而受限制。即,推測陰離子水溶性高分子(B)具有分散劑的功能,除去研磨畢研磨對象物上所殘留的雜質。另外,所謂「側鏈」係指由「主鏈」分支出的鏈。
鹽(特別係相對陽離子)並無特別的限制,可例如銨鹽、鈉鹽等。
磺酸基或其鹽的基、或者羧基或其鹽的基當作側鏈時,係可直接鍵結於僅由上述碳原子構成的主鏈,亦可經由其他連接基,鍵結於僅由上述碳原子構成的主鏈上。上述連接基係可列舉例如碳數6~24個的伸芳基、二價酸醯胺等。另外,碳數6~24個的伸芳基較佳係伸苯基、萘二基等。
所示,R12、R13及R15係各自獨立為氫原子、碳數1~12之烷基、碳數1~12之羥烷基或相對陽離子;R14係二價基。根據該實施形態,可效率佳地達成本發明所期待效果。
此處,碳數1~12的烷基係可為直鏈狀、亦可為分支狀,例如:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基(undecyl group)、十二烷基、十三烷基、十四烷基、十六烷基、硬脂基、廿烷基、廿二烷基、廿四烷基、卅烷基、異丙基、異丁基、第三丁基、異戊基、新戊基、第三戊基、異庚基、2-乙基己基、異癸基。
再者,碳數1~12的羥烷基係可列舉例如上述碳數1~12的烷基中之至少1個氫原子被取代為羥基者。
再者,二價基係可列舉例如碳數1~12之伸烷基、碳數6~24個的伸芳基等。碳數1~12之伸烷基係上述碳數1~12之烷基經去除1個氫的2價取代基。又,碳數6~24個的伸芳基較佳係伸苯基、萘二基等。
再者,相對陽離子係可列舉例如銨離子、鈉離子等。
本形態的(1)中,R9係氫原子或甲基,R10及R11分別係-COOR12、氫原子,R12係氫原子或相對陽離子。此時,特別較佳係pH未滿7.0、更佳係未滿5.0。
再者,本形態的(2)中,上述陰離子水溶性高分子(B)係含有:R9為氫原子或甲基,R10及R11分別為-COOR12、氫原子,R12為氫原子或相對陽離子的構成單元;以及R9為氫原子或甲基,R10及R11均為-COOR12,R12為氫原子或相對陽 離子的構成單元。此時,亦可為無水物的形熊。
再者,本形態的(3)中,R9係氫原子或甲基,R10及R11均係-COOR12,R12係氫原子或相對陽離子。
再者,本形態的(4)中,上述陰離子水溶性高分子(B)係含有:R9為氫原子或甲基,R10及R11分別為-COOR12、氫原子,R12為氫原子或相對陽離子的構成單元;以及R9為氫原子或甲基,R10及R11中之至少其中一者為-COOR12,R12為碳數1~12的羥烷基之構成單元。
再者,本形態的(5)中,上述陰離子水溶性高分子(B)係含有:R9為氫原子或甲基,R10及R11中之至少其中一者為-COOR12,R12為氫原子或相對陽離子的構成單元;以及R9為氫原子或甲基,R10及R11中之至少其中一者為-G,而-G係
所示,R14為二價基,R15為氫原子、碳數1~12之烷基、碳數1~12之羥烷基或相對陽離子。
所示,R13係氫原子、碳數1~12之烷基、碳數1~12之羥烷基或相對陽離子。
所示,R14係二價基,R15係氫原子、碳數1~12之烷基、碳數1~12之羥烷基或相對陽離子。
尤其,就從達成本發明所期待效果的觀點,較佳係本形態的(1)或(2)、更佳係本形態的(1)。此時,如上述,特別較佳係pH未滿7.0、更佳係未滿5.0。
所示,R13係同上述,該陰離子水溶性高分子(B)的重量平均分子量係10萬以上。根據該實施形態,可效率佳地達成本發明所期待效果。
本發明中,陰離子水溶性高分子(B)的重量平均分子量,就從充分除去缺陷的觀點,較佳係400以上、更佳係1,000以上、特佳係2,000以上、最佳係2,500以上。又,亦可達8,000 以上、亦可達10,000以上、亦可達30,000以上、亦可達50,000以上、亦可達80,000以上、亦可達100,000以上。又,就從充分除去缺陷的觀點,較佳係1,000,000以下、更佳係900,000以下、亦可在300,000以下、亦可在150,000以下、亦可在80,000以下。又,為能更有效地獲得本發明所期待效果,較佳係50,000以下、更佳係30,000以下、特佳係10,000以下、最佳係8,000以下。
另外,重量平均分子量係利用凝膠滲透色層分析儀(GPC),以已知分子量的聚苯乙烯為基準物質進行測定。
陰離子水溶性高分子(B)的含有量,就從充分除去缺陷的觀點,相對於表面處理組合物的總質量,較佳係0.01質量%以上、更佳係0.05質量%以上。又,較佳係5質量%以下、更佳係1質量%以下、特佳係0.6質量%以下、最佳係0.3質量%以下、最佳係0.2質量%以下。
(pH)
本發明表面處理組合物的pH係未滿9.0。若pH達9.0以上,便無法達成本發明所期待效果。另外,pH值係採用依實施例方法所測定的值。
本發明表面處理組合物的pH在未滿9.0之前提下,其餘並無特別的限制,較佳係未滿8.0、更佳係未滿7.0、特佳係未滿6.0、亦可未滿4.0、亦可未滿3.5。根據本發明較佳實施形態,表面處理組合物的pH係未滿7.0。又,本發明表面處理組合物的pH較佳係1.5以上、更佳係2.0以上。
調整pH時,最好使用pH調整劑。該pH調整劑係可使用習知的酸、鹼、或該等的鹽。
可使用為pH調整劑的酸之具體例,係可列舉例如鹽酸、硫酸、硝酸、氫氟酸、硼酸、碳酸、次磷酸、亞磷酸、及磷酸等無機酸;甘醇酸、葡糖酸、衣康酸、蟻酸、醋酸、丙酸、丁酸、戊酸、2-甲基丁酸、己酸、3,3-二甲基-丁酸、2-乙基丁酸、4-甲基戊酸、庚酸、2-甲基己酸、辛酸、2-乙基己酸、苯甲酸、羥醋酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、苯二甲酸(phthalic acid)、蘋果酸、酒石酸、檸檬酸、乳酸、二甘醇酸、2-呋喃羧酸、2,5-呋喃二羧酸、3-呋喃羧酸、2-四氫呋喃羧酸、甲氧基醋酸、甲氧苯基醋酸、及苯氧醋酸等有機酸。當pH調整劑係使用無機酸時,就從提升研磨速度的觀點,較佳係硫酸、硝酸、磷酸等,當pH調整劑係使用有機酸時,較佳係甘醇酸、琥珀酸、順丁烯二酸、檸檬酸、酒石酸、蘋果酸、葡糖酸、及衣康酸等。
可使用為pH調整劑的鹼,係可列舉例如:脂肪族胺、芳香族胺等胺;銨溶液、氫氧化第四銨等有機鹼;氫氧化鉀等鹼金屬的氫氧化物;第IIA族元素的氫氧化物;組胺酸等胺基酸;氨等。
該等pH調整劑之中,就從pH調整的容易性、更降低雜質的觀點,更佳係硝酸、銨溶液、組胺酸等胺基酸。
pH調整劑係可單獨使用、或組合2種以上使用。pH調整劑的添加量並無特別的限制,只要依研磨用組合物成為所需pH的方式適當調整便可。
(分散介質)
本發明一形態的表面處理組合物通常係含有分散介質(溶劑)。分散介質係具有使各成分分散或溶解的功能。分散介質較佳係僅為水。又,分散介質係為能使各成分分散或溶解,亦可為水與有機溶劑的混合溶劑。
水係就從抑制表面處理對象物的污染、以及其他成分作用的觀點,最好係盡可能未含雜質的水。例如較佳係過渡金屬離子的合計含有量在100ppb以下的水。此處,水的純度係藉由例如:使用離子交換樹脂施行的雜質離子除去、利用過濾器施行的異物除去、以及利用蒸餾等操作便可提高純度。具體而言,水較佳係使用例如:去離子水(離子交換水)、純水、超純水、蒸餾水等。
(其他添加劑)
本發明一形態的表面處理組合物,在不致阻礙本發明效果之範圍內,視需要亦可依任意比例含有其他的添加劑。但,因為會成為雜質的原因,因而添加量較佳係盡可能少、更佳係未含有。其他添加劑係可列舉例如防腐劑、溶解氣體(dissolved gas)、還原劑、氧化劑等。
另外,本發明的表面處理組合物較佳係未含研磨顆粒(磨粒)。
(表面處理組合物之製造方法)
另外,本發明係提供下述表面處理組合物之製造方法,該表面處理組合物係使用於研磨畢研磨對象物之表面處理,係使非離子水溶性高分子(A)與陰離子水溶性高分子(B)混合,且pH未滿9.0,並含有矽-矽鍵與氮-矽鍵;而該非離子水溶性高分子(A)係具有僅由碳原子構成、或由碳原子與氮原子構成的主 鏈;該陰離子水溶性高分子(B)係具有主鏈與側鏈,該主鏈係僅由碳原子構成,該側鏈係鍵結於該僅由碳原子構成的主鏈,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基。
上述表面處理組合物的製造方法並無特別的限制,藉由將構成表面處理組合物的各成分、及視需要的其他成分,利用分散介質施行攪拌混合便可獲得。各成分混合時的溫度並無特別的限制,較佳係10~40℃,為能提升溶解速度,亦可施行加熱。又,混合時間亦無特別的限制。
(研磨畢研磨對象物之表面處理方法)
依如上述,藉由使用本發明的表面處理組合物,從研磨畢研磨對象物的表面上除去雜質,便可使該研磨畢研磨對象物(基板)表面的表面狀態變化。該方法稱「表面處理方法」。所以,本發明亦提供研磨畢研磨對象物之表面處理方法,包括使用上述表面處理組合物,施行研磨畢研磨對象物之表面處理。
表面處理方法係除使用上述表面處理組合物之外,其餘均可使用一般的方法。可列舉例如將研磨畢研磨對象物(以下亦稱「表面處理對象物」)浸漬於表面處理組合物中的方法;施行超音波處理的方法;或者將表面處理對象物一邊使用墊施行旋轉處理,一邊使表面處理組合物流動的方法等。墊係可使用一般的不織布、聚氨酯、及多孔質氟樹脂等,並無特別的限制均可使用。
表面處理裝置係安裝有:保持研磨畢研磨對象物等的支撐架、與能變更旋轉數的馬達等,具有能黏貼墊之研磨定盤的一般研磨裝置。
此處,一邊使用墊施行旋轉處理,一邊使表面處理組合物流動的方法時,處理條件亦無特別的限制,例如研磨畢研磨對象物與墊間之的壓力較佳係0.5~10psi。研磨頭旋轉數較佳係10~100rpm。又,定盤旋轉數較佳係10~100rpm。流動的供應量並無限制,最好表面處理對象物的表面被表面處理組合物覆蓋,例如10~5000ml/分鐘。又,表面處理時間亦無特別的限制,較佳係5~180秒鐘。
根據此種範圍,可更良好地除去雜質。
表面處理時,表面處理組合物的溫度並無特別的限制,通常可為室溫,但在不致損及性能之範圍內,亦可加溫至40℃以上、70℃以下的程度。
(水洗步驟)
本發明中,利用水施行的水洗步驟係可在本發明的表面處理方法之前或之後實施,亦可前後均有實施。
例如,可針對經施行過表面處理之一面,使用毛刷(例如聚乙烯醇製),並使用純水,依旋轉數10~200rpm施行10~120秒鐘的水洗。然後,依旋轉數100~2000rpm、10~120秒鐘,使經施行表面處理過的研磨畢研磨對象物旋轉而乾燥。
(半導體基板之製造方法)
本發明中,CMP步驟施行對象的研磨對象物,係含有矽-矽鍵、與氮-矽鍵,較佳係可提供作為半導體基板者。經CMP步驟後的研磨畢研磨對象物的表面上會有雜質殘留,但藉由本發明的表面處理組合物充分地除去研磨畢研磨對象物表面的缺陷而製造半導體基板,便不會對半導體的電特性造成不良影 響,可提升裝置可靠度。
即,本發明亦提供半導體基板之製造方法,係包括依照上述表面處理方法,對研磨畢研磨對象物的表面施行處理。藉由上述表面處理方法對經CMP步驟後被研磨過的研磨對象物(研磨畢研磨對象物)的表面施行處理,便可製造有效降低雜質的半導體基板,並能抑制半導體電特性的不良影響,可提升裝置可靠度。
另外,本發明的表面處理組合物係適用於含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物之表面處理,且pH未滿9.0,含有:具有僅由碳原子構成、或由碳原子與氮原子所構成主鏈的非離子水溶性高分子(A);以及具有主鏈與側鏈的陰離子水溶性高分子(B);而,該主鏈係僅由碳原子構成,該側鏈係鍵結於該僅由碳原子構成的主鏈,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基。意味著本發明的表面處理組合物亦適用於含有矽-矽鍵及氮-矽鍵中之至少其中一者的研磨畢研磨對象物之表面處理。所以,本案亦提供下述表面處理組合物,係使用於含有矽-矽鍵及氮-矽鍵中之至少其中一者的研磨畢研磨對象物之表面處理,且pH未滿9.0,含有:具有僅由碳原子構成、或由碳原子與氮原子所構成主鏈的非離子水溶性高分子(A);以及具有主鏈與側鏈的陰離子水溶性高分子(B);而,該主鏈係僅由碳原子構成,該側鏈係鍵結於該僅由碳原子構成的主鏈,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基。該表面處理組合物的具體說明係可適用上述。
實施例
針對本發明使用以下實施例與比較例進行更詳細說明。但,本發明技術範圍並不僅侷限於以下實施例。另外,實施例中,使用「份」或「%」表示時,在無特別聲明的前提下係表示「質量份」或「質量%」。又,在無特別記載的前提下,各操作均在室溫(25℃)下實施。
<研磨畢研磨對象物之準備>
研磨對象物係準備12吋多晶矽晶圓(厚度:20×103Å)、及12吋氮化矽晶圓(厚度:3×103Å),將該等研磨對象物分別利用下述研磨用漿料A,且依下述研磨條件施行研磨,而獲得各研磨畢研磨對象物。
(漿料A)
將各原料,依照混合溫度:約25℃、混合時間:約10分鐘,在純水中施行混合,而獲得含有磨粒(膠體二氧化矽;平均一次粒徑:35nm、平均二次粒徑:70nm)2質量%、與PVP 0.1質量%的漿料A。
(研磨條件)
研磨裝置:荏原製作所製FREX 300E
研磨墊:Dow IC1010
研磨頭旋轉數:91rpm
研磨定盤旋轉數:90rpm
研磨畢研磨對象物與研磨墊間之壓力:2psi
研磨用組合物供應量:300ml/分鐘
研磨用組合物之供應:流動
研磨時間:1分鐘。
<實施例1>
(表面處理組合物之製備)
將成分1之表1所示PVA(成分(A))、成分2之表1所示聚(甲基丙烯酸鈉鹽)(成分(B))、以及pH調整劑之硝酸,依成為表1所示組成的方式,在純水中混合,而製備表面處理組合物(混合溫度:約25℃、混合時間:約3分鐘)。另外,實施例、比較例所使用「PVA」的皂化度為95%以上。
pH係利用pH儀(堀場製作所公司製,型號:LAQUA)確認(液溫:25℃)。
重量平均分子量係採用以聚苯乙烯為標準物質,利用凝膠滲透色層分析儀(GPC)測定的值。
(表面處理步驟)
針對依上述所準備的各研磨畢研磨對象物,使用依照上述製備的表面處理組合物,依照下述表面處理條件施行表面處理。
(表面處理條件)
表面處理裝置:荏原製作所製FREX 300E
研磨墊:Dow IC1010
研磨頭旋轉數:61rpm
定盤旋轉數:60rpm
研磨畢研磨對象物與研磨墊間之壓力:1psi
表面處理組合物供應量:300ml/分鐘
表面處理組合物之供應:流動
表面處理時間:1分鐘。
(水洗步驟)
對經施行過表面處理之一面,使用聚乙烯醇製毛刷,利用純水依旋轉數100rpm施行50秒鐘的水洗。然後,依旋轉數1500rpm,使經施行表面處理過的研磨畢研磨對象物進行旋轉60秒鐘,而施行乾燥。
(缺陷數之評價)
經施行表面處理、及水洗後的研磨畢研磨對象物12吋晶圓中全面的缺陷(關於多晶矽晶圓係達0.23μm以上者,關於氮化矽晶圓係達0.16μm以上)數,係使用KLA TENCOR公司製SP-1進行評價。
具體而言,LPD(large particle distribution,大粒子分佈)值係利用暗視野測定(Dark-field composited oblique channel)實施。結果如表1所示。
LPD值越高則表示缺陷性能越差,但若多晶矽晶圓中的缺陷數在360個以下、且氮化矽晶圓中的缺陷數在820個以下,便可判斷為缺陷數充分少,具有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物,係可提供作為半導體基板用。
另外,實施例中,分別使用多晶矽晶圓與氮化矽晶圓進行評價,但可估計使用具有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物之情況,仍可獲得同樣的評價結果。
<其他的實施例與比較例>
與實施例1同樣地,藉由將表1所示成分、與視情況所需的pH調整劑進行混合,而製備表面處理組合物。然後,依照與上述同樣的方法,施行表面處理、水洗,並進行評價。結果如表1所示。
(考察)
根據本發明的表面處理組合物,因為多晶矽晶圓中的缺陷數在360個以下、且氮化矽晶圓中的缺陷數在820個以下,因而暗示可充分除去具有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷。相對於此,若使用比較例的組合物,因為多晶矽晶圓中的缺陷數超過360個、或氮化矽晶圓中的缺陷數超過820個,因而暗示無法充分除去具有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物表面之缺陷。
另外,本申請案係根據2016年9月21日所提出申請的日本專利申請案第2016-184768號為基礎,參照其揭示內容並全體援用。
Claims (11)
- 一種表面處理組合物,係含有:非離子水溶性高分子(A),其乃具有僅由碳原子構成、或由碳原子與氮原子構成的主鏈;以及陰離子水溶性高分子(B),其乃具有主鏈與側鏈,而該主鏈係僅由碳原子構成;該側鏈係鍵結於該僅由碳原子構成的主鏈上,且具有磺酸基或其鹽之基、或具有羧基或其鹽之基;使用於含有矽-矽鍵與氮-矽鍵的研磨畢研磨對象物之表面處理,且pH未滿9.0,其中該表面處理組合物包括分散介質,且該分散介質僅為水。
- 如申請專利範圍第1或2項中任一項所述之表面處理組合物,其中,上述非離子水溶性高分子(A)係從:聚乙烯醇(PVA)、構造之其中一部分含有源自聚乙烯醇(PVA)之構成單元的共聚物、聚乙烯吡咯烷酮(polyvinylpyrrolidone;PVP)、構造之其中一部分含有源自聚乙烯吡咯烷酮(PVP)之構成單元的共聚物、聚乙烯己內醯胺、構造之其中一部分含有源自聚乙烯己內醯胺之構成單元的共聚物、聚N-乙烯基甲醯胺、及構造之其中一部分含有源自聚N-乙烯基甲 醯胺之構成單元的共聚物所構成群組中選擇至少1種。
- 如申請專利範圍第1或2項所述之表面處理組合物,其中,上述非離子水溶性高分子(A)係聚乙烯醇(PVA)、或構造之其中一部分含有聚乙烯醇(PVA)之構成單元的共聚物。
- 如申請專利範圍第4項所述之表面處理組合物,其中,上述聚乙烯醇(PVA)、或構造之其中一部分含有上述聚乙烯醇(PVA)之構成單元的共聚物之皂化度為60%以上。
- 如申請專利範圍第1或2項所述之表面處理組合物,其中,pH係未滿7.0。
- 一種研磨畢研磨對象物之表面處理方法,係使用申請專利範圍第1至8項中任一項所述之表面處理組合物,施行研磨畢研磨對象物的表面處理。
- 如申請專利範圍第9項所述之研磨畢研磨對象物之表面處理方法,其中該研磨畢研磨對象物含有矽-矽鍵與氮-矽鍵。
- 一種半導體基板之製造方法,係依照申請專利範圍第9或10項所述之表面處理方法,對研磨畢研磨對象物的表面施行處理。
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- 2017-08-09 SG SG11201901590SA patent/SG11201901590SA/en unknown
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JPWO2018055941A1 (ja) | 2019-07-04 |
KR102305256B1 (ko) | 2021-09-29 |
SG11201901590SA (en) | 2019-03-28 |
WO2018055941A1 (ja) | 2018-03-29 |
CN109716487A (zh) | 2019-05-03 |
US20190203027A1 (en) | 2019-07-04 |
JP6880047B2 (ja) | 2021-06-02 |
KR20190055089A (ko) | 2019-05-22 |
TW201814034A (zh) | 2018-04-16 |
US11326049B2 (en) | 2022-05-10 |
CN109716487B (zh) | 2023-12-01 |
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