TWI656205B - 研磨用組成物及使用其之研磨方法 - Google Patents
研磨用組成物及使用其之研磨方法 Download PDFInfo
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- TWI656205B TWI656205B TW104107910A TW104107910A TWI656205B TW I656205 B TWI656205 B TW I656205B TW 104107910 A TW104107910 A TW 104107910A TW 104107910 A TW104107910 A TW 104107910A TW I656205 B TWI656205 B TW I656205B
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
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- UJQLBTVHLKVNCC-UHFFFAOYSA-M sodium;4-(2-methylprop-2-enoylamino)benzenesulfonate Chemical compound [Na+].CC(=C)C(=O)NC1=CC=C(S([O-])(=O)=O)C=C1 UJQLBTVHLKVNCC-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- 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
- H01L21/302—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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
本發明提供一種可充分消除SiN膜之階差之研磨用組成物。
本發明係一種研磨用組成物,其係在研磨於pH未達6之條件下表面帶正電之研磨對象物之用途所用,且包含水、研磨粒、與具有特定單位構造之陰離子性共聚物,且pH未達6,前述陰離子性共聚物具有酸性度不同之2種以上之酸性基。
Description
本發明係關於半導體裝置造製程中使用之研磨用組成物及使用其之研磨方法。
半導體裝置製造製程中,隨著半導體裝置之性能提升,需要更高密度且高積體地製造配線之技術。該半導體裝置之製造製程中之CMP(Chemical Mechanical Polishing;化學機械研磨)成為必要製程。隨著半導體電路之微細化進展,圖型晶圓之凹凸所要求之平坦性變高,要求藉由CMP而實現奈米級之高平坦性。為了藉CMP而實現高的平滑性,較好以高的研磨速度研磨圖型晶圓之凸部,另一方面不研磨凹部。
此處,使用由氮化矽膜(SiN膜)所成之圖型晶圓時,氮化矽膜通常具有凹凸,故研磨該材料時,不僅凸部被研削,凹部也一起被研削,不易完全消除凹凸。
再者,半導體晶圓係由形成電路之多結晶矽、絕緣材料的氧化矽、與用以保護並非溝槽或通孔之一部分之二氧化矽表面在蝕刻中免於損傷之氮化矽之異種材
料所構成。因此,會引起多結晶矽或氧化矽等較柔軟之易與研磨劑反應之材料比其周圍之氮化矽等更被過度研削之凹陷現象,而留有階差。
由此在由較硬且化學安定之氮化矽等材料所成之圖型晶圓之研磨步驟中要求充分消除階差。
為因應該要求之技術例如於日本特表2009-530811號公報(美國專利申請公開第2007/209287號說明書)中揭示一種包含(a)研磨劑、(b)丙二酸0.1mM~10mM、(c)胺基羧酸0.1mM~100mM、(d)硫酸離子0.1mM~100mM、及(e)水,且pH為1~6之組成物,作為同時研磨含鎢之電路材料與硬塗層的氮化鈦二者之用途中使用之化學機械研磨用組成物。
又,特開2012-040671號公報(美國專利申請公開第2013/146804號說明書)中揭示一種研磨用組成物,其係相較於多結晶矽等可更高速研磨氮化矽等缺乏化學反應性之研磨對象物之研磨用組成物,其係含有經固定化有機酸之膠體二氧化矽,且pH為6以下之研磨用組成物。
然而,過去之研磨用組成物之問題為在半導體研磨步驟中無法充分消除SiN膜等所具有之凹凸。
因此本發明之目的係提供一種可充分消除SiN膜之階差之研磨用組成物。
為解決上述課題,本發明人重複積極研究。結果,發現使用與研磨粒一起含有特定陰離子性共聚物之酸性研磨用組成物,可對於在未達pH6下表面帶正電之氮化矽之凸部以相對於凹部特別高的研磨速度進行研磨。因此,基於上述見解,終於完成本發明。
亦即,本發明係一種研磨用組成物,其係研磨於pH未達6之條件下表面帶正電之研磨對象物之用途中使用,其包含水、研磨粒、與具有以下述通式1或下述通式2表示之單位構造之陰離子性共聚物,且pH未達6,前述陰離子性共聚物具有酸性度不同之2種以上之酸性基。
(上述通式1中,Q1為氫;選自由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基所組成之群之碳數1~6之烷基;選自由甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基等所組成之群選出之碳數1~6之烷氧基,Q1’為單鍵、醚鍵、酯鍵、醯胺鍵、羰基鍵之任一者,
x為0~10之整數,y為0~10之整數,X為選自磺酸基、羧基、羥基、或磷酸基之酸性基,或具有至少1個該等酸性基之碳數1~10之脂肪族烴基,或具有至少1個前述酸性基之碳數6~12之芳香族烴基)。
(上述通式2中,Ar為經取代或無取代之碳數6~12之芳香族基,Ar為經取代之芳香族基時,取代基列舉為選自由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基所組成之群之碳數1~6之烷基;選自由甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基等所組成之群選出之碳數1~6之烷氧基,Q2為單鍵、醚鍵、酯鍵、醯胺鍵、羰基鍵之任一者,x為0~10之整數,y為0~10之整數,Y為選自磺酸基、羧基、羥基、或磷酸基之酸性基,或具有至少1個該等酸性基之碳數1~10之脂肪族烴基,或具有至少1個前述酸性基之碳數6~12之芳香族烴
基)。
以下,說明本發明。
本發明之第一項係研磨在研磨時所使用之研磨用組成物之pH區域中表面帶正電之研磨對象物之用途中使用之包含研磨粒、具有以上述通式1表示之單位構造或以上述通式2表示之單位構造之陰離子性共聚物,且pH未達6之研磨用組成物。藉由成為該構成,可高選擇性地削除包含具有凹凸之SiN膜之圖型晶圓之凸部,因而可充分消除圖型晶圓之階差。
藉由使用本發明之研磨用組成物,可高選擇性地削除包含具有凹凸之SiN膜之圖型晶圓之凸部之詳細理由並不清楚,但推測為以下機制。
首先在pH未達6之條件下氮化矽之研磨對象物表面帶正電,另一方面二氧化矽等研磨粒表面之羥基經質子化,使表面之負電荷變少。陰離子性共聚物所具有之酸性度不同之複數種酸性基中,酸性度較低而不易離子化之酸性基顯示與二氧化矽等研磨粒表面之親和性。另一方面,如磺酸基之酸性度較高而容易離子化之酸性基顯示與水相或具有正電荷之被研磨對象物之親和性。
該種陰離子性共聚物靜電吸附於帶正電荷之
研磨對象物上,但凸部因與研磨粒之衝撞而承受研磨壓力,因研磨壓力使陰離子性共聚物與研磨粒相互牽引故凸部之陰離子性共聚物比凹部更容易自研磨對象物表面去除。因此在凸部以陰離子性共聚物無影響地進行研磨。另一方面,凹部不易與立體的研磨粒衝撞,容易留下吸附有陰離子性共聚物之層,故認為係研磨速度受抑制者。
又,上述之機制為推測者,本發明不受上述機制之任何限制。
本發明之研磨用組成物中所含之陰離子性共聚物具有酸性度不同之2種以上之酸性基,且較好具有2種酸性度不同之酸性基,更好一併具有對研磨用組成物之pH為高的酸解離常數之酸性基,與對研磨用組成物之pH為低的酸解離常數之酸性基。若具有酸性度不同之2種以上之酸性基,則該陰離子性共聚物之單位構造可為僅以通式1或通式2之任一者表示,亦可為具有以通式1表示之單位構造與以通式2表示之單位構造兩者。X及Y亦可為構造相同之酸性基。此外,前述陰離子性共聚物亦可具有3種以上之單位構造。
本發明之研磨用組成物藉由包含前述陰離子性共聚,而對於氮化矽等在pH未達6之條件下表面帶正電之研磨對象物表面之凹凸之凸部具有高選擇性研削作用。例如,依據本發明之較佳一實施形態,係提供一種具
有對於在pH未達6之條件下表面帶正電之研磨對象物表面之凸部,以相對於凹部為10倍以上之研磨速度進行研磨之步驟之研磨方法或基板之製造方法。
前述陰離子性共聚物可為具有酸性基之2種以上之單體之共聚物,亦可為使具有能變換成酸性基之官能基之2種以上之單體共聚合後將該等官能基變換成酸性基者。共聚物可為無規共聚物、交互共聚物、嵌段共聚物、接枝共聚物之任一種,但較好為酸性基根據每種類而偏向存在之嵌段共聚物。
又,本發明之研磨用組成物所含有之陰離子性共聚物只要具有以下述通式1表示之單位構造或以下述通式2表示之單位構造者即無特別限制,可為乙烯系共聚物,亦可為縮合系共聚物。前述陰離子性共聚物可使用市售品,亦可於市售之樹脂中導入酸性基。
(上述通式1中,Q1為氫;選自由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基所組成之群之碳數1~6之烷基;選自由甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基等所組成之群選出
之碳數1~6之烷氧基,Q1’為單鍵、醚鍵、酯鍵、醯胺鍵、羰基鍵之任一者,x為0~10之整數,y為0~10之整數,X為選自磺酸基、羧基、羥基、或磷酸基之酸性基,或具有至少1個該等酸性基之碳數1~10之脂肪族烴基,或具有至少1個前述酸性基之碳數6~12之芳香族烴基)。
(上述通式2中,Ar為經取代或無取代之碳數6~12之芳香族基,Ar為經取代之芳香族基時,取代基列舉為選自由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基所組成之群之碳數1~6之烷基;選自由甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基等所組成之群選出之碳數1~6之烷氧基,Q2為單鍵、醚鍵、酯鍵、醯胺鍵、羰基鍵之任一者,x為0~10之整數,y為0~10之整數,
Y為選自磺酸基、羧基、羥基、或磷酸基之酸性基,或具有至少1個該等酸性基之碳數1~10之脂肪族烴基,或具有至少1個前述酸性基之碳數6~12之芳香族烴基)。
另所謂單鍵意指藉由共有1組共價電子對而顯示鍵結,故Q1’或Q2表示單鍵時,Q1’或Q2上不含碳原子等之原子,Q1’或Q2之兩相鄰之原子相互以單鍵鍵結。
陰離子性共聚物具有之顯示相互不同之酸性度之酸性基或鍵結有酸性基之取代基之構造可相同亦可不同。不同酸性基之較佳組合列舉為磺酸基與羧酸基之組合。且,為相同酸性基或鍵結有相同酸性基之取代基時,亦可因主鏈之構造互不相同而展現酸性度差異。例如丙烯酸與富馬酸之共聚物之情況下,係由以-CH(COOH)-表示之單位構造與以-CH2CH(COOH)-表示之單位構造所成。該情況下,前者之單位構造藉由鍵結於酸性基所鄰接之碳上,於脫離質子後殘留之負電荷因鄰接之酸性基而安定化,促進了酸性基之質子脫離。因此,即使使用具有不同酸性度之酸性基或鍵結有酸性基之取代基為相同構造之陰離子性共聚物時,認為仍可獲得本發明之效果。
陰離子性共聚物之分子量,基於保護作用之觀點較好為500以上,更好為1000以上。且,基於分散性之觀點,較好為100000以下,更好為50000以下。又,重量平均分子量可藉GPC(凝膠滲透層析儀)測定。
陰離子性共聚物於本發明之研磨用組成物之
含量可依據研磨粒之含量或研磨對象適當調整,並無特別限制,但可為0.1~100000ppm之範圍。若為該範圍,則可以充分之研磨速度使氮化矽等研磨對象物平坦化。
陰離子性共聚物之酸性度不同之酸性基之至少1種酸性基之酸解離常數(pKa)對於研磨用組成物之pH較好較小。藉由使至少1種酸性基之酸解離常數(pKa)對於研磨用組成物之pH較小,可使陰離子性共聚物離子化,而容易吸附於研磨對象物上。因此,可抑制凹部因研磨粒而被削除。
本發明之研磨用組成物所含有之陰離子性共聚物可藉過去習知之方法合成,例如,可藉以下方法製造。
(1)對苯乙烯、乙烯基甲苯、乙烯基萘等之可導入陰離子性基之單體之共聚物,或對該等單體與乙烯基化合物單體之共聚物導入陰離子性基之方法
上述可導入陰離子性基之單體列舉為例如乙二醇或聚乙二醇之二丙烯酸酯或二甲基丙烯酸酯、苯乙烯、乙烯基甲苯、乙烯基碸、乙烯基萘等。
例如,可藉由使苯乙烯與二乙烯基苯之交聯共聚物磺化,製造本發明中使用之陰離子性共聚物。
以該等方法進行之陰離子性共聚物之調製中可使用之上述乙烯基化合物單體並無特別限制,列舉為例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)
丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥基丙酯、甲基丙烯酸縮水甘油酯、丙烯酸縮水甘油酯等丙烯酸酯或甲基丙烯酸酯及乙酸乙烯酯等乙烯酯類,或丙烯腈、甲基丙烯腈等,2-甲基苯乙烯、第三丁基苯乙烯、氯苯乙烯、乙烯基苯甲醚、二乙烯基苯等芳香族乙烯類,偏氯化乙烯、偏氟化乙烯等偏鹵化乙烯類,乙烯、丙烯、異丙烯丁二烯、乙烯基吡咯啶酮、氯化乙烯、乙烯基醚、乙烯基酮、氯丁二烯、丙烯腈、丁二烯、氯丁二烯等。
(2)使甲基丙烯酸、甲基丙烯酸甲酯、馬來酸酐、乙烯基磺酸、乙烯基磺酸甲酯、對-苯乙烯磺酸、對-苯乙烯磺酸甲酯等具有陰離子性基之乙烯基化合物共聚合之方法,或者使具有該等陰離子性基之乙烯基化合物與上述乙烯基化合物單體共聚合之方法
該方法中亦可視需要使不具有離子性基之單體共聚合,或者使所得共聚物中之羧酸酯、磺酸酯水解而調製離子交換容量(陽離子交換容量)。
以該方法進行之陰離子性共聚物之調製中可使用之具有陰離子性基之乙烯基化合物並無特別限制,列
舉為例如下述者。
具有羧基之乙烯基化合物列舉為例如丙烯酸、甲基丙烯酸、巴豆酸、異巴豆酸、2-乙基丙烯酸、3-第三丁基丙烯酸等丙烯酸系單體;馬來酸、甲基馬來酸、苯基馬來酸、氯馬來酸、富馬酸、衣康酸、黏康酸等馬來酸系單體。
具有磺酸基之乙烯基化合物列舉為例如2-丙烯醯胺丙烷磺酸、2-丙烯醯胺-正丁烷磺酸、2-丙烯醯胺-正己烷磺酸、2-丙烯醯胺-正辛烷磺酸、2-丙烯醯胺-正十二烷磺酸、2-丙烯醯胺-2-甲基丙烷磺酸、2-丙烯醯胺-2-苯基丙烷磺酸、2-丙烯醯胺-2,4,4-三甲基戊烷磺酸、2-丙烯醯胺-2-(4-氯苯基)丙烷磺酸、2-甲基丙烯醯胺-正十四烷磺酸、4-甲基丙烯醯胺苯磺酸鈉、甲基丙烯酸2-磺乙酯、對-乙烯基苯磺酸、苯乙烯磺酸、伸乙基磺酸、乙烯基磺酸等。
具有羥基之乙烯基化合物列舉為例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸3-羥基-2-乙基己酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、甲基丙烯酸縮水甘油酯-(甲基)丙烯酸加成物、1,1,1-三羥甲基丙烷或丙三醇之二(甲基)丙烯酸酯等。
具有磷酸基之乙烯基化合物列舉為例如乙烯基膦酸、(甲基丙烯醯氧基乙基)磷酸酯、二苯基-2-丙烯醯氧基乙基磷酸酯、二苯基-2-甲基丙烯醯氧基乙基磷酸酯、二丁基-2-丙烯醯氧基乙基磷酸酯等。
該方法中,具有陰離子性基之酚類可例示為苯酚磺酸、萘酚磺酸、對-羥基苯磺酸、水楊酸鈉等。又,醛類係使用福馬林、聚甲醛、乙二醛、呋喃甲醛類等。該情況下,為了調整陽離子交換容量,亦可使用苯酚、甲酚、萘酚、間苯二酚等作為共聚合成分。
該方法中,可藉由例如使2,6-萘二羧酸或其酯形成性衍生物、間苯二甲酸或其酯形成性衍生物及5-鈉磺基間苯二甲酸或其酯形成性衍生物,與四亞甲基二醇、9,9-雙[4-(2-羥基乙氧基)苯基]茀、雙酚A環氧乙烷加成物成分反應形成單體或寡聚物,隨後在真空下聚縮合藉此調製聚酯。如此合成之聚酯隨後亦可導入酸性基,亦可預先於單體中導入能轉變成酸性基之取代基,於聚縮合後轉變成酸性基。
該方法中,可使用之含有酸性基之芳香族二鹵化物可列舉為4,4’-二氯二苯基碸、4,4’-二氟二苯基碸、4,4’-二氯二苯基酮、4,4’-二氯二苯基苯基氧化膦、4,4’-二氟二苯基苯基氧化膦等。
該方法中可使用之二羧酸二鹵化物列舉為對苯二甲酸氯化物、2-氯對苯二甲酸氯化物、2,5-二氯對苯二甲酸氯化物、2,6-二氯對苯二甲酸氯化物、2,6-萘二羧酸氯化物,可使用之二胺列舉為對-苯二胺、2-氯對-苯二胺、2,5-二氯對-苯二胺、2,6-二氯對-苯二胺、間-苯二胺、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸等芳香族二胺等。
本發明之研磨用組成物中所含之研磨粒為具有機械研磨研磨對象物之作用,且提高研磨用組成物對研磨對象物之研磨速度。
使用之研磨粒可為無機粒子、有機粒子及有機無機複合粒子之任一種。無機粒子列舉為例如由二氧化矽、氧化鋁、氧化鈰、氧化鈦等金屬氧化物所成之粒子,
以及氮化矽粒子、碳化矽粒子、氮化硼粒子。有機粒子之具體例列舉為例如聚甲基丙烯酸甲酯(PMMA)粒子。該研磨粒可單獨使用亦可混合2種以上使用。另外,該研磨粒可使用市售品亦可使用合成品。
該等研磨粒中,以二氧化矽較佳,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之表面電荷接近於零,故在酸性條件下二氧化矽粒子彼此間不會靜電排斥而容易引起凝聚。相對於此,即使在未達pH6之酸性條件下表面仍帶負電之經表面修飾之研磨粒在酸性條件下相互間亦強烈排斥而成良好分散之結果,提高了研磨用組成物之保存安定性。如此之表面修飾研磨粒可藉由例如使鋁、鈦或鋯等金屬或該等之氧化物與研磨粒混合而摻雜於研磨粒之表面之方法,或於二氧化矽表面導入磺酸等酸性官能基之方法而獲得。其中,較佳者為摻雜Al(鋁)之二氧化矽或固定有有機酸之膠體二氧化矽。
獲得摻雜Al之二氧化矽之方法可使用於膠體二氧化矽之分散液中添加鋁酸鈉之方法。該方法詳細記載於日本專利第3463328號公報、日本特開昭63-123807號公報中,該記載可適用於本發明。
固定化有有機酸之膠體二氧化矽係藉由例如使有機酸之官能基化學鍵結於膠體二氧化矽表面而進行。僅單使膠體二氧化矽與有機酸共存,無法達到有機酸朝膠
體二氧化矽之固定化。使有機酸之一種的磺酸固定化於膠體二氧化矽上可藉例如“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)中所記載之方法調製。具體而言,使3-巰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,藉此可獲得磺酸固定化於表面之膠體二氧化矽。或者,若使羧酸固定化於膠體二氧化矽上,則可藉例如“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)中所記載之方法進行。具體而言,在將含有光反應性2-硝基苄酯之矽烷偶合劑偶合於膠體二氧化矽後,藉由光照射,可獲得使羧酸固定化於表面之膠體二氧化矽。
研磨粒之平均一次粒徑之下限較好為5nm以上,更好為7nm以上,又更好為10nm以上。且,研磨粒之平均一次粒徑之上限較好為500nm以下,更好為250nm以下,又更好為100nm以下。若為該範圍,則研磨用組成物對研磨對象物之研磨速度提高,且可進一步抑制使用研磨用組成物研磨後之研磨對象物表面產生研磨傷痕(刮痕)。又,研磨粒之平均一次粒徑係採用例如基於以BET法測定之研磨粒之比表面積而算出。
研磨粒之平均二次粒徑之上限較好為500nm以下,更好為400nm以下,又更好為300nm以下。研磨
粒之平均二次粒徑之值可以例如雷射光散射法側定。
研磨粒之平均二次粒徑之下限較好為5nm以上,更好為7nm以上,又更好為10nm以上。
研磨粒之平均二次粒徑之值除以平均一次粒徑之值獲得之研磨粒平均締合度(degree of association)較好為1以上,更好為1.2以上。隨著研磨粒之平均締合度變大,有提高以研磨用組成物對於研磨對象物之去除速度之優點。
且研磨粒之平均締合度較好為5以下,更好為4以下,又更好為3以下。隨著研磨粒之平均締合度變小,使用研磨用組成物研磨研磨對象物時容易獲得表面缺陷少之研磨面。
研磨用組成物中之研磨粒含量之下限較好為0.05質量%以上,更好為0.5質量%以上,又更好為1質量%以上,最好為2質量%以上。且,研磨用組成物中之研磨粒之含量上限較好為50質量%以下,更好為30質量%以下,又更好為20質量%以下。若為該範圍,則可提高研磨對象物之研磨速度,且可抑制研磨用組成物之成本。
本發明之研磨用組成物之pH值未達6。pH值為6以上時,由於如氮化矽之研磨對象物表面之正電荷變小,故使用表面帶負電之研磨粒以高速度研磨研磨對象物亦變得困難。基於利用研磨用組成物以充分之研磨速度研磨氮化
矽等研磨對象物之觀點,研磨用組成物之pH值較好為5以下,更好為4以下,最好為3以下。
研磨用組成物之pH值基於安全性之觀點較好為1以上,更好為1.5以上。
為了將研磨用組成物之pH調整成期望之值,本發明之研磨用組成物含有pH調整劑。pH調整劑可使用如下述之酸或螯合劑。
酸列舉為例如甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉荳蔻酸、棕櫚酸、十七烷酸、硬脂酸、油酸、亞油酸、亞麻酸、花生四烯酸、二十二碳六烯酸、二十碳五烯酸、乳酸、蘋果酸、檸檬酸、苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、水楊酸、沒食子酸、苯六甲酸(mellitic acid)、桂皮酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、富馬酸、馬來酸、烏頭酸、胺基酸、硝基羧酸等羧酸,或甲烷磺酸、乙烷磺酸、苯磺酸、對-甲苯磺酸、10-樟腦磺酸、羥乙基磺酸、牛磺酸等磺酸。又,列舉碳酸、鹽酸、硝酸、磷酸、次磷酸、亞鄰酸、磺酸、硫酸、硼酸、氫氟酸、原鄰酸、焦磷酸、多磷酸、偏磷酸、六偏磷酸等無機酸。
螯合劑列舉為多元胺、聚膦酸、聚胺基羧酸、聚胺基膦酸等。
該等pH調整劑可單獨使用亦可混合2種以上使用。該等pH調整劑中,以無機酸、羧酸較佳。
pH調整劑之添加量並無特別限制,只要以成為上述pH範圍之方式適當選擇添加量即可。
本發明之研磨用組成物包含水。基於防止因雜質對研磨用組成物之其他成分之影響之觀點,較好使用儘可能高純度之水。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。且,亦可進一步含有有機溶劑等作為分散介質或溶劑以控制研磨用組成物之其他成分之分散性等。
本發明之研磨用組成物亦可視需要進一步包含錯化劑、金屬防腐蝕劑、防腐劑、防黴劑、氧化劑、還原劑、界面活性劑、水溶性高分子等其他成分。以下針對氧化劑、防腐劑、防黴劑、水溶性高分子加以說明。
可添加於研磨用組成物之氧化劑具有使研磨對象物之表面氧化之作用,且提高研磨用組成物對研磨對象物之研磨速度。
可使用之氧化劑列舉為過氧化氫、過氧化鈉、過氧化鋇、有機氧化劑、臭氧水、銀(II)鹽、鐵(III)鹽、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、過鄰苯二甲酸、次氯酸、次溴酸、次碘酸、氯酸、亞氯酸、過氯酸、氫溴酸、氫碘酸、過碘酸、過硫酸、二氯異氰尿酸及該等之鹽等。該等氧化劑可單獨使用亦可混合2種以上使用。該等中,以過氧化氫、過硫酸銨、過碘酸、次氯酸及二氯異氰尿酸鈉較佳。
研磨用組成物中之氧化劑含量較好為0.1g/L以上,更好為1g/L以上,又更好為3g/L以上。隨著氧化劑含量變多,可更提高研磨用組成物對研磨對象物之研磨速度。
研磨用組成物中之氧化劑含量較好為200g/L以下,更好為100g/L以下,又更好為40g/L以下。隨著氧化劑含量減少,除了可抑制研磨用組成物之材料成本以外,亦可減輕研磨使用後之研磨用組成物之處理亦即廢棄處理之負荷。且,亦可減少因氧化劑造成之研磨對象物表面之過度氧化之虞。
本發明之研磨用組成物中可添加之防腐劑及防黴劑列舉為例如2-甲基-4-異噻唑啉-3-酮或5-氯-2-甲基-4-異噻唑啉-3-酮等之異噻唑啉系防腐劑,對羥基苯甲酸酯類、及苯氧基乙醇等。該等防腐劑及防黴劑可單獨使用或亦可混合2種以上使用。
本發明之研磨用組成物中,以提高研磨對象物表面之親水性或提高研磨粒之分散安定性為目的,亦可添加水溶性高分子。水溶性高分子列舉為羥基甲基纖維素、羥基乙基纖維素(HEC)、羥基丙基纖維素、羥基乙基甲基纖維素、羥基丙基甲基纖維素、甲基纖維素、乙基纖維素、乙基羥基乙基纖維素、羧基甲基纖維素等纖維素衍生物;聚(N-醯基伸烷基亞胺)等亞胺衍生物;聚乙烯醇;改質(陽離子改質,或非離子改質)聚乙烯醇;聚乙烯吡咯啶酮;聚乙烯基己內醯胺;聚氧伸乙基等聚氧基伸烷基類等;以及含該等構成單位之共聚物。該等水溶性高分子可單獨使用,亦可混合2種以上使用。
本發明之研磨用組成物之製造方法並無特別限制,可攪拌混合例如研磨粒、具有以上述通式1表示之單位構造或以上述通式2表示之單位構造之陰離子性共聚物、pH調整劑、水及視需要之其他成分而獲得。
混合各成分時之溫度並無特別限制,較好為10~40℃,亦可加熱以提高溶解速度。
本發明之被研磨材料只要在pH未達6之條件下表面帶正電之研磨對象物即無特別限制,列舉為例如包含氮化
矽等氮化物、鋁-鎂、矽-鍺等合金、或該等之複合材料等之研磨對象物之被研磨材料。該等研磨對象物可單獨或2種以上之組合。又,研磨對象物可為單層構造,亦可為2種以上之多層構造。多層構造時,各層可含相同材料,亦可含不同材料。
被研磨材料之表面在pH未達6之條件下是否帶正電可藉由測定在將pH調整成未達6之溶液中之被研磨材料,或由與該被研磨材料相同成分所成之粒子之Zeta電位加以判斷。
又,在pH未達6之條件下表面帶正電之研磨對象物只要是在pH未達6之條件下具有帶正電之pH區域之物質即可,並不需要在未達6之pH區域中全域中帶正電。
再者,本發明之被研磨材料亦可具有上述研磨對象物、及含有與前述研磨對象物不同之材料之層。
與前述研磨對象物不同之材料之例列舉為例如多晶矽、單晶矽、原矽酸四乙酯(TEOS)、矽氧化物等。該等材料可單獨或2種以上之組合。又,含有與研磨對象物不同之材料之層可為單層構造亦可為2種以上之多層構造。多層構造之情況下,各層可含相同材料,亦可含不同材料。
如上述,本發明之研磨用組成物可較好地用於氮化矽
等在pH未達6之條件下表面帶正電之研磨對象物之研磨。因此,本發明之第二項係使用本發明之研磨用組成物研磨在pH未達6之條件下表面帶正電之研磨對象物之研磨方法。此外,本發明之第三項係包含以前述研磨方法研磨在pH未達6之條件下表面帶正電之研磨對象物之步驟之基板的製造方法。
使用本發明之研磨用組成物研磨在pH未達6之條件下表面帶正電之研磨對象物時,可使用通常金屬研磨所用之裝置或條件進行。一般之研磨裝置有單面研磨裝置與雙面研磨裝置。單面研磨裝置係使用稱為載具之保持具保持基板,邊自上方供給研磨用組成物,邊將貼附有研磨墊之壓盤按壓於基板之對向面且使壓盤旋轉,藉此研磨被研磨材料之單面。此時,利用研磨墊及研磨用組成物、與被研磨材料之磨擦所致之物理作用,與研磨用組成物對於被研磨材料之化學作用而研磨。前述研磨墊可無特別限制地使用不織布、聚胺基甲酸酯、羊毛氈等多孔質體。研磨墊中較好施以可使研磨液積存之加工。
本發明之研磨方法之研磨條件列舉為研磨荷重、壓盤轉數、載具轉數、研磨用組成物之流量、研磨時間。該等研磨條件並無特別限制,但例如關於研磨荷重,基板之每單位面積較好為0.1psi以上10psi以下,更好為0.5psi以上8.0psi以下,又更好為1.0psi以上6.0psi以下。一般而言荷種愈高研磨粒之摩擦力愈高,而提高機械加工力故提高研磨速度。若在該範圍,則可發揮充分之研
磨速度,可抑制因荷重造成之基板破損、或表面產生傷痕等之缺陷。壓盤轉數及載具轉數較好為10~500rpm。研磨用組成物之供給量只要能覆蓋被研磨材料之基板整體之供給量即可,只要依據基板之大小等條件予以調整即可。
本發明之研磨用組成物可為一液型,亦可為以二液型為代表之多液型。且,本發明之研磨用組成物亦可藉由使用水等稀釋液將研磨用組成物之原液稀釋至例如10倍以上而調整。
使用以下之實施例及比較例詳細說明本發明。但,本發明之技術範圍並不僅限於以下之實施例。
在水中混合表3所示之量之作為研磨粒之表1所示之膠體二氧化矽、及陰離子性共聚物,以pH調整劑調整pH,獲得研磨用組成物(混合溫度約25℃,混合時間:約10分鐘)。研磨用組成物之pH係以pH計確認。
又,表3所示之研磨粒及研磨對象物之種類係如下述表1。
[表1].研磨粒A:摻雜Al之二氧化矽(平均一次粒徑:35nm,平均二次粒徑:68nm)B:表面固定有磺酸之膠體二氧化矽(平均一次粒徑:35nm,平均二次粒徑:68nm).被研磨材料氮化矽(SiN)
使用本發明之研磨用組成物,測定藉以下研磨條件研磨研磨對象基板時之研磨速度。
[表2].研磨條件研磨機:日本ENGIS公司製造之桌上研磨機EJ-380IN研磨墊:聚胺基甲酸酯製墊研磨壓力:1.2psi(凹部)、3.9psi(凸部)壓盤轉數:60rpm研磨用組成物之流量:100ml/min膜厚測定器:光干涉式膜厚測定裝置
研磨速度係由以下之式計算。
研磨速度[Å/min]=研磨1分鐘時之膜厚變化量
研磨速度之測定結果示於下述表3。又,表3中之研磨速度比為凸部之研磨速度除以凹部之研磨速度所算出之值。
由上述表3之研磨速度比之結果可了解,使用實施例1~10之本發明之研磨用組成物時,確定研磨對象物的氮化矽膜之凸部相對於凹部係高選擇性地削除。
另一方面,未添加有機化合物之研磨用組成物(比較例1)、使用非離子性有機高分子之研磨用組成物(比較例2、3)、使用具有強酸性基之均聚物之研磨用組成物(比較例4~6)、雖使用陰離子性共聚物但pH為6之研磨用組成物(比較例7)均無法獲得高的研磨速度,未見到選擇性削除凸部之作用。
又,本申請案係基於2014年3月28日申請之日本專利申請案第2014-69265號,其揭示內容全文以參照加以援用。
Claims (5)
- 一種研磨用組成物,其係在研磨於pH未達6之條件下表面帶正電之研磨對象物之用途所用者,其包含水、研磨粒、與具有以下述通式1或下述通式2表示之單位構造之陰離子性共聚物,且該研磨用組成物之pH未達6,前述研磨粒在未達pH6下係表面帶負電,前述陰離子性共聚物具有酸性度不同之2種以上之酸性基,(上述通式1中,Q1為氫;選自由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基所組成之群之碳數1~6之烷基;選自由甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基等所組成之群選出之碳數1~6之烷氧基,Q1’為單鍵、醚鍵、酯鍵、醯胺鍵、羰基鍵之任一者,x為0~10之整數,y為0~10之整數,X為選自磺酸基、羧基、羥基、或磷酸基之酸性基,或具有至少1個該等酸性基之碳數1~10之脂肪族烴基,或具有至少1個前述酸性基之碳數6~12之芳香族烴基),(上述通式2中,Ar為經取代或無取代之碳數6~12之芳香族基,Ar為經取代之芳香族基時,取代基列舉為選自由甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基所組成之群之碳數1~6之烷基;選自由甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基所組成之群選出之碳數1~6之烷氧基,Q2為單鍵、醚鍵、酯鍵、醯胺鍵、羰基鍵之任一者,x為0~10之整數,y為0~10之整數,Y為選自磺酸基、羧基、羥基、或磷酸基之酸性基,或具有至少1個該等酸性基之碳數1~10之脂肪族烴基,或具有至少1個前述酸性基之碳數6~12之芳香族烴基)。
- 如請求項1之研磨用組成物,其中前述陰離子性共聚物係具有以前述通式1表示之單位構造之乙烯系共聚物。
- 如請求項1或2之研磨用組成物,其中前述研磨對象物為包含氮化矽之基板。
- 一種研磨方法,其具有對於在pH未達6之條件下表面帶正電之研磨對象物表面的凸部,以相對於凹部為10倍以上之研磨速度使用如請求項1~3中任一項之研磨用組成物進行研磨之步驟。
- 一種基板之製造方法,其包含以如請求項4之研磨方法進行研磨之步驟。
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