TW201402732A - 硏磨用組成物 - Google Patents
硏磨用組成物 Download PDFInfo
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- TW201402732A TW201402732A TW102108840A TW102108840A TW201402732A TW 201402732 A TW201402732 A TW 201402732A TW 102108840 A TW102108840 A TW 102108840A TW 102108840 A TW102108840 A TW 102108840A TW 201402732 A TW201402732 A TW 201402732A
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
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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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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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
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- 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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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
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Abstract
本發明之研磨用組成物為使用於研磨具有相變合金之研磨對象物之用途之研磨用組成物,其特徵為含有選自於下述化合物之至少1種以上,而前述化合物為分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物。
Description
本發明為有關適合於研磨具有相變合金之研磨對象物之研磨用組成物。
PRAM(相變隨機存取記憶體)裝置(已知亦作為雙向記憶體裝置或PCRAM裝置)中,用於電子記憶用途在絕緣性非晶質相與傳導性結晶性相之間,係利用著能電性切換之相變材料(PCM)。適合於此等用途之典型相變材料,係以週期表之各種的VIB族(硫屬化物(chalcogenide),例如Te或Po)及VB族(例如Sb)元素,與In、Ge、Ga、Sn或Ag等之1種或複數種之金屬元素之組合而被利用著。特別適合的相變材料為鍺(Ge)-銻(Sb)-碲(Te)合金(GST合金)。此等材料為依附於(depend on)加熱/冷卻速度、溫度、及時間,而可使物理狀態可逆性地變化。其他適合的合金為包含銻化銦(InSb)。PRAM裝置中的記憶資訊會依不同物理之相或狀態之傳導特性,使損失成為最小地予以保存。
作為研磨半導體基材(例如,積體電路)之含有金屬之表面之方法,已知有化學機械研磨(CMP)。在CMP所使用的研磨用組成物,典型為含有研磨粒、氧化劑、錯化劑,並有效地利用蝕刻來進行研磨。
如此般的CMP,可利用於用來製作使用相變材料的記憶裝置。然而,不似由單一成分諸如銅(Cu)或鎢(W)所成的以往的金屬層,被研磨之相變材料係將硫(S)、鈰(Ce)、鍺(Ge)、銻(Sb)、碲(Te)、銀(Ag)、銦(In)、錫(Sn)、鎵(Ga)等,以結晶相及非結晶質相為可逆性進行相變化之特定比例混合而成,大多的相變材料(例如,GST)之物理性質,相較於PCM晶片中所利用的其他材料為「軟質」之點等,由於與以往的金屬層材料之特性不同,故難以將現今用來研磨含有金屬之表面之研磨用組成物直接予以適用。
如此般狀況之中,對於適合研磨具有相變合金之研磨對象物之研磨用組成物,已進行各種之檢討。例如,專利文獻1及2中已揭示一種以研磨具有相變合金之研磨對象物作為目的之研磨用組成物,其係包含研磨粒、錯化劑、水及任意的氧化劑。此等之發明為將用來研磨以往含有金屬之表面的典型研磨用組成物予以改良,使成為能降低表面缺陷或相變材料之殘渣之研磨用組成物。但,僅以此等發明時,作為以研磨具有相變合金之研磨對象物為目的之研磨用組成物而言為不充分,乃期待進一步的改良。
〔專利文獻1〕日本特表2010-534934號公報
〔專利文獻2〕日本特表2009-525615號公報
在此,本發明之目的,係以提供一種在研磨具有相變合金之研磨對象物之用途為可適合使用的研磨用組成物。特別是提供,一種可抑制凹坑(recess)產生的研磨用組成物。即,將用來研磨以往含有金屬之表面的典型研磨用組成物予以改良時,對於相變合金會引起過度之蝕刻,其結果方面會產生凹坑,並發現所謂的使原本應為殘留的凸塊部分溶出之新課題,本發明即以提供能解決此等課題的研磨用組成物。
本發明團隊在經過精心探討後,結果發現到一種研磨用組成物,其係藉由包含選自於下述化合物之至少1種以上,其中前述化合物為分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,而可為於具有相變合金之研磨對象物抑制凹坑之產生。
即,本發明之要旨為如同下述。
<1>一種研磨用組成物,其係使用於研磨具有相變合金之研磨對象物之用途之研磨用組成物,其特徵為包含選
自於下述化合物之至少1種以上,而前述化合物為分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物。
<2>如上述<1>之研磨用組成物,其中具有上述特定構造之化合物為一般式(1)所示的β-二酮化合物。
<3>如上述<1>之研磨用組成物,其中具有上述特定構造之化合物為式(2)所示的β-酮醯胺化合物。
<4>如上述<1>之研磨用組成物,其中具有上述特定構造之化合物為式(3)所示的β-酮酯化合物。
<5>如上述<1>~<4>中任一項之研磨用組成物,其係進而包含研磨粒。
<6>如上述<5>之研磨用組成物,其中研磨粒為膠體矽石。
<7>如上述<1>~<6>中任一項之研磨用組成物,其係使用於研磨具有GST作為相變合金之研磨對象物之用途。
<8>一種研磨方法,其特徵係使用上述<1>~<6>中任一項之研磨用組成物來研磨具有相變合金之研磨對象物之表面。
<9>一種基板之製造方法,其特徵係具有使用上述<1>~<6>中任一項之之研磨用組成物來研磨具有相變合金之研磨對象物之表面之步驟。
藉由本發明,可提供一種研磨用組成物,其係能適合使用於研磨具有相變合金之研磨對象物之用途。特別是提供一種有效抑制凹坑之產生的研磨用組成物。
以下為說明本發明之一實施形態。
本實施形態之研磨用組成物為包含選自於下述化合物之至少1種以上,而前述化合物為分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物。然後,本實施形態之研磨用組成物係提供作為一種有效抑制凹坑之產生的研磨用組成物。所謂的凹坑,係指由於研磨用組成物中所包含之成分,使研磨對象物,特別是相變合金引起過度蝕刻,而溶出之缺陷。
此研磨用組成物為使用於研磨具有相變合金之研磨對象物之用途。相變合金,在PRAM(相變隨機存取記憶體)裝置(已知亦作為雙向記憶體裝置或PCRAM裝置)中,用於電子記憶用途在絕緣性非晶質相與傳導性結晶性相之間,係利用著能電性切換之材料。作為適合於此等用途之相變合金,係以週期表之各種的VIB族(硫屬化物,例如Te或Po)及VB族(例如Sb)元素,與In、Ge、Ga、Sn或Ag等之1種或複數種之金屬元素之組合而被利用著。特別適合的相變材料為鍺(Ge)-銻(Sb)-碲(Te)合金(GST合金)。
如同前述,作為研磨半導體基材(例如積體電路)之
含有金屬之表面的方法,已知有CMP。在CMP所使用的研磨用組成物,典型為含有研磨粒、氧化劑、錯化劑,而有效地利用蝕刻來進行研磨。如此般的CMP,可利用於用來製作使用相變材料的記憶裝置。然而,不似由單一成分(例如Cu、W)所成的以往的金屬層,被研磨之相變材料係將S、Ce、Ge、Sb、Te、Ag、In、Sn、Ga等,以結晶相及非結晶質相為可逆性進行相變化之特定比例混合而成,大多的相變材料(例如,GST)之物理性質,相較於PCM晶片中所利用的其他材料為「軟質」之點等,由於與以往的金屬層材料之特性不同,故難以將用來研磨以往典型的含有金屬之表面之研磨用組成物直接予以適用。特別是,將用來研磨以往含有金屬之表面的典型研磨用組成物予以改良時,對於相變合金會引起過度之蝕刻,其結果方面會產生凹坑。又,依GST之種類而異,有以水亦能產生蝕刻者。
研磨用組成物,作為藉由如後述所說明的機制而對於相變合金為具有金屬防蝕效果之化合物,係含有選自於下述化合物之至少1種以上,而前述化合物為分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物。雖凹坑之產生之機制尚不明確,但係認為如下:因以往的研磨用組成物中的添加劑(特別是錯化劑)等,
使對於相變合金引起過度的氧化反應,其結果方面由於相變合金之氧化物會溶出,因而產生了凹坑。相較於此,分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,係相變合金與化合物(其係分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物)之分子內的2個羰基會鍵結而形成不溶性的錯合物,因而於相變合金表面形成不溶性的脆性膜。其結果認為,抑制了因以往的研磨用組成物中的添加劑(特別是錯化劑)等之對於相變合金之過度蝕刻,而可抑制凹坑。
研磨用組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,列舉例如下述式(1)~式(3)所示的化合物,其中下述一般式(1)所示的β-二酮化合物:
(其中,一般式(1)中,R1、R2、R3及R4示為氫原子、選自於具有1~4個碳原子之烷基、羥基乙基、及可經取代之芳基的1官能基,或是示為形成包含R1與R3及/或R2與R4之五節環或六節環之構造);下述一般式(2)所示的β-酮醯胺化合物:
(其中,一般式(2)中,R5、R6、R7、R8及R9示為氫原子、選自於具有1~4個碳原子之烷基、羥基乙基、及可經取代之芳基的1官能基,或是示為形成包含R5與R6、R6與R7、R7與R9、及R8與R9中任1組以上之五節環或六節環之構造);及下述一般式(3)所示的β-酮酯化合物:
(其中,一般式(3)中,R10、R11、R12及R13示為氫原子、選自於具有1~4個碳原子之烷基、羥基乙基、及可經取代之芳基的1官能基,或是示為形成包含R10與R11、R11與R12、及R12與R13中任1組以上之五節環或六節環之構造)。
研磨用組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,當該化合物為前述一般式(1)所示的β-二酮化合物時,具體舉例如乙醯丙酮、三氟乙醯丙酮、丙醯丙酮、苯甲醯丙酮、苯甲醯三氟丙酮、二苯甲醯甲烷。此等可單獨使用1
種,亦可組合2種以上使用。
研磨用組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,當該化合物為前述一般式(2)所示的β-酮醯胺化合物時,具體舉例如N-甲基乙醯乙醯胺(N-methylacetoacetamide)、N,N-二甲基乙醯乙醯胺、N-(2-羥基乙基)乙醯乙醯胺、乙醯乙醯胺苯(acetoacetanilide)、N-(2-甲基苯基)乙醯乙醯胺、N-(4-甲氧基苯基)乙醯乙醯胺、N-(4-氯苯基)乙醯乙醯胺、及3-氧代戊醯胺(3-oxopentanamide)。此等可單獨使用1種,亦可組合2種以上使用。
研磨用組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,當該化合物為前述一般式(3)所示的β-酮酯化合物時,具體舉例如乙醯乙酸甲酯、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、乙醯乙酸十八烷基酯、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。此等可單獨使用1種,亦可組合2種以上使用。
研磨用組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,該化合物之含有量之上限較佳為10質量%,又較佳為8質量%,更佳為5質量%。隨著分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物之含有量減少,由於研磨速度會提昇,故宜。
研磨用組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,該化合物之含有量之下限較佳為0.0001質量%,又較佳為0.001質量%,更佳為0.01質量%。隨著分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物之含有量增加,會抑制蝕刻。其結果由於可抑制凹坑之產生,故宜。
研磨用組成物可進而含有研磨粒。研磨粒可為無機粒子、有機粒子、及有機無機複合粒子中之任一種。作為無機粒子的具體例,例如可列舉出由矽石、氧化鋁、氧化鈰、氧化鈦等之金屬氧化物所構成之粒子,以及氮化矽粒子、碳化矽粒子及氮化硼粒子。作為有機粒子的具體例,例如可列舉出聚甲基丙烯酸甲酯(PMMA)粒子。當中較佳為矽石粒子,特佳為膠體矽石。
研磨粒可經表面改質。一般的膠體矽石,由於在酸性條件下動電勢之值接近於零,所以在酸性條件下,矽石粒子彼此不會相互呈電相斥而容易凝聚。相對於此,即使在酸性條件下動電勢亦具有相對較大的正或負值之經表面改質之研磨粒,在酸性條件下亦可彼此強力相斥而良好地分散,其結果可提昇研磨用組成物的保存穩定性。此般經表面改質之研磨粒,例如可將鋁、鈦或鋯等之金屬或此等的氧化物與研磨粒混合,使摻雜於研磨粒的表面而得。
或是,研磨用組成物中之經表面改質之研磨粒,亦可為將有機酸固定化之矽石。當中較佳可使用將有機酸固定化之膠體矽石。有機酸對膠體矽石之固定化,是藉由將有機酸的官能基化學鍵結於膠體矽石的表面來進行。僅使膠體矽石與有機酸共存者,乃無法達成有機酸對膠體矽石之固定化。將有機酸的一種之磺酸固定化於膠體矽石者,例如可藉由“Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”,Chem.Commun.246-247(2003)所記載之方法來進行。具體而言,可在將3-巰丙基三甲氧矽烷等之具有硫醇基之矽烷偶合劑偶合於膠體矽石後,以過氧化氫將硫醇基氧化而得到磺酸固定化於表面之膠體矽石。或是,將羧酸固定化於膠體矽石者,例如可藉由“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)所記載之方法來進行。具體而言,可將含有光反應性的2-硝基苄酯之矽烷偶合劑偶合於膠體矽石後,進行光照射而得到羧酸固定化於表面之膠體矽石。
研磨用組成物中,研磨粒之含有量較佳為0.1質量%以上,又較佳為0.5質量%以上,更佳為1質量%以上。隨著研磨粒的含有量增多,具有可提昇藉由研磨用組成物之研磨對象物之除去速度之優點。
研磨用組成物中,研磨粒之含有量較佳為20質量%
以下,又較佳為15質量%以下,更佳為10質量%以下。隨著研磨粒的含有量減少,可抑制研磨用組成物的材料成本,並且不易引起研磨粒的凝聚。此外,藉由使用研磨用組成物來研磨研磨對象物,可容易得到表面缺陷少之研磨面。
研磨粒的平均一次粒徑,較佳為5nm以上,又較佳為7nm以上,更佳為10nm以上。隨著研磨粒的平均一次粒徑增大,有利於提昇藉由研磨用組成物之研磨對象物之除去速度。尚,研磨粒的平均一次粒徑之值,例如可根據由BET法所測定之研磨粒的比表面積來計算。
研磨粒的平均一次粒徑,較佳為100nm以下,尤佳為90nm以下,更佳為80nm以下。隨著研磨粒的平均一次粒徑減少,藉由使用研磨用組成物來研磨研磨對象物,可容易得到表面缺陷少之研磨面。
研磨粒的平均二次粒徑,較佳為150nm以下,又較佳為120nm以下,更佳為100nm以下。研磨粒的平均二次粒徑之值,例如可藉由雷射光散射法來測定。
研磨粒之以平均一次粒徑之值除上平均二次粒徑之值所得之研磨粒的平均結合度(degree of association),較佳為1.2以上,又較佳為1.5以上。隨著研磨粒的平均結合度增大,具有可提昇藉由研磨用組成物之研磨對象物之除去速度之優點。
研磨粒的平均結合度,較佳為4以下,又較佳為3以下,更佳為2以下。隨著研磨粒的平均結合度降低,藉由
使用研磨用組成物來研磨研磨對象物,可容易得到表面缺陷少之研磨面。
研磨用組成物之pH之上限未特別特限定,但較佳為12,又較佳為10。隨著pH變低,研磨用組成物之操作性會提昇。
研磨用組成物之pH之下限,亦未特別特限定,但較佳為1,又較佳為3。當pH越高時,越可提昇研磨用組成物中研磨粒之分散性。
為了將研磨用組成物之pH調整成所希望之值,因應所需而使用的pH調整劑可任意為酸或鹼,又,亦可為任意的無機或有機之化合物。
研磨用組成物中可進而含有氧化劑。氧化劑為具有將研磨對象物之表面氧化之作用,當研磨用組成物中添加有氧化劑時,藉由研磨用組成物之研磨速度具有提昇之效果。然而,當研磨對象物為具有相變合金,若使用用來研磨以往含有金屬之表面的典型研磨用組成物來進行研磨時,會引起過度研磨。此可考量為相變合金之特性與以往半導體中所使用的金屬(例如,Cu)之特性不同之故,當研磨對象物為具有相變合金時,氧化劑之含有量較佳為低者。
研磨用組成物中,氧化劑之含有量之上限,較佳為10質量%,又較佳為5質量%。隨著氧化劑之含有量減少,不易因氧化劑而產生相變合金之過剩氧化,可抑制過度研磨。
研磨用組成物中,氧化劑之含有量之下限,較佳為0.1質量%,又較佳為0.3質量%。隨著氧化劑之含有量增加,有助於研磨速度之提昇。
可使用的氧化劑,例如有過氧化物。作為過氧化物之具體例,列舉例如過氧化氫、過乙酸、過碳酸鹽、過氧化尿素及過氯酸,以及過硫酸鈉、過硫酸鉀及過硫酸銨等之過硫酸鹽。之中就研磨速度之觀點而言,較佳為過硫酸鹽及過氧化氫;就在水溶液中的穩定性及環境負荷之觀點而言,特佳為過氧化氫。
研磨用組成物中可進而含有錯化劑。研磨用組成物中所包含的錯化劑,係具有將相變合金的表面化學性蝕刻之作用,而具有提昇藉由研磨用組成物之研磨速度之功用。然而,當研磨對象物為具有相變合金,若使用用來研磨以往含有金屬之表面的典型研磨用組成物來進行研磨時,會引起過剩蝕刻,該結果會引起過度研磨。此可考量為相變合金之特性與以往半導體中所使用的金屬(例如,Cu)之特性不同之故,當研磨對象物為具有相變合金時,錯化劑之含有量較佳為低者。
研磨用組成物中,錯化劑之含有量之上限,較佳為10質量%,又較佳為1質量%。隨著錯化劑之含有量減少,不易因錯化劑而產生對於相變合金之過剩蝕刻。該結果可抑制過剩研磨。
研磨用組成物中,錯化劑之含有量之下限,較佳為0.01質量%,又較佳為0.1質量%。隨著錯化劑之含有量增加,對於相變合金之蝕刻效果會增加。該結果,有助於藉由研磨用組成物之研磨速度之提昇。
可使用的錯化劑,有例如無機酸、有機酸、及胺基酸。作為無機酸之具體例,列舉例如硫酸、硝酸、硼酸、碳酸、次磷酸、亞磷酸及磷酸。作為有機酸的具體例,例如可列舉出甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、n-己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、n-庚酸、2-甲基己酸、n-辛酸、2-乙基庚酸、苯甲酸、乙醇酸、柳酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸及乳酸。亦可使用甲烷磺酸、乙烷磺酸及2-羥乙磺酸(isethionic acid)等之有機硫酸。此外,亦可使用無機酸或有機酸的鹼金屬鹽等之鹽,來取代無機酸或有機酸、或是與無機酸或有機酸組合使用。作為胺基酸的具體例,例如可列舉出甘胺酸、α-丙胺酸、β-丙胺酸、N-甲基甘胺酸、N,N-二甲基甘胺酸、2-胺基丁酸、正纈胺酸、纈胺酸、白胺酸、正白胺酸、異白胺酸、苯基丙胺酸、脯胺酸、肌胺酸、鳥胺酸、離胺酸、牛磺酸、絲胺
酸、蘇胺酸、類絲胺酸、酪胺酸、蠶豆苷(vicine)、麥黃酮(tricine)、3,5-二碘-酪胺酸、β-(3,4-二羥苯基)-甘胺酸、甲狀腺素、4-羥基-脯胺酸、半胱胺酸、甲硫胺酸、乙硫胺酸、羊毛硫胺酸、胱硫醚、胱胺酸、氧化半胱胺酸(cysteic acid)、天門冬胺酸、麩胺酸、S-(羧甲基)-半胱胺酸、4-胺基丁酸、天門冬胺、麩胺、偶氮絲胺酸、精胺酸、刀豆氨酸、瓜氨酸、δ-羥基-離胺酸、肌酸、組胺酸、1-甲基-組胺酸、3-甲基-組胺酸、及色胺酸。之中作為錯化劑,就提昇研磨之觀點而言較佳為甘胺酸、丙胺酸、蘋果酸、酒石酸、檸檬酸、乙醇酸、2-羥乙磺酸或是此等之鹽。
研磨用組成物中可進而含有金屬防蝕劑。當將金屬防蝕劑添加於研磨用組成物時,使用研磨用組成物進行研磨後之相變合金,具有不易產生碟狀凹陷(dishing)等表面缺陷之效果。此外,該金屬防蝕劑,當研磨用組成物中為包含氧化劑及/或錯化劑時,可緩和因氧化劑所造成的相變合金表面之氧化,且與金屬離子(其係因氧化劑所造成的相變合金表面之金屬之氧化所產生者)反應,而發揮生成不溶性的錯合物之功用。其結果可抑制因錯化劑所造成的對相變合金之蝕刻,並可抑制過度研磨。
可使用的金屬防蝕劑之種類未特別特限定,但較佳為雜環化合物。雜環化合物中的雜環之節數未特別特限定。
又,雜環化合物可為單環化合物,亦可為具有縮合環之多環化合物。
作為金屬防蝕劑之雜環化合物之具體例,列舉例如吡咯化合物、吡唑化合物、咪唑化合物、三唑化合物、四唑化合物、吡啶化合物、吡嗪化合物、噠嗪化合物、4-氮茚化合物、吲哚嗪化合物、吲哚化合物、異吲哚化合物、吲唑化合物、嘌呤化合物、喹嗪化合物、喹啉化合物、異喹啉化合物、萘啶化合物、酞嗪化合物、喹喔啉化合物、喹唑啉化合物、噌啉化合物、蝶啶化合物、噻唑化合物、異噻唑化合物、噁唑化合物、異噁唑化合物及呋呫化合物等之含氮雜環化合物。作為吡唑化合物的具體例,例如可列舉出1H-吡唑、4-硝基-3-吡唑羧酸及3,5-吡唑羧酸。作為咪唑化合物的具體例,例如可列舉出咪唑、1-甲基咪唑、2-甲基咪唑、4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-異丙基咪唑、苯並咪唑、5,6-二甲基苯並咪唑、2-胺基苯並咪唑、2-氯苯並咪唑及2-甲基苯並咪唑。作為三唑的具體例,例如可列舉出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、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、1-羥基苯並三唑、1-胺基苯並三唑、1-羧基苯並三唑、5-氯-1H-苯並三唑、5-硝基-1H-苯並三唑、5-羧基-1H-苯並三唑、5,6-二甲基-1H-苯並三唑、1-(1",2'-二羧乙基)苯並三唑。作為四唑化合物的具體例,例如可列舉出1H-四唑、5-甲基四唑、5-胺基四唑、及5-苯基四唑。作為吲哚化合物的具體例,例如可列舉出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、及7-甲基-1H-吲哚。作為吲唑化合物的具體例,例如可列舉出1H-吲唑及5-胺基-1H-吲唑。此等雜環化合物,由於對相變合金之化學或物理吸附力高,所以可將更堅固的保護膜形成於相變合金表面。因此,可抑制在使用研磨用組成物進行研磨後之相變合金的過剩蝕刻。其結果可抑制過剩研磨。
研磨用組成物中,金屬防蝕劑之含有量之上限,較佳為10質量%,又較佳為5質量%,更佳為1質量%。隨著金屬防蝕劑之含有量減少,藉由研磨用組成物之研磨速度具有提昇之效果。
研磨用組成物中,金屬防蝕劑之含有量之下限,較佳為0.001質量%,又較佳為0.01質量%,更佳為0.1質量%。隨著金屬防蝕劑之含有量增加,可抑制在使用研磨用組成物進行研磨後之相變合金的過剩蝕刻。其結果可抑制過剩研磨。
本發明之其他實施形態為提供一種研磨方法,其係使用本發明之研磨用組成物用來研磨具有相變合金之研磨對
象物之表面。作為可在本研磨方法中使用之墊片(pads),可使用不織布、發泡聚胺基甲酸酯(PU)、多孔質氟樹脂等,並無特別限制。此外,可在研磨墊片上施以溝槽加工以使研磨用組成物容易停留在研磨墊片上。
研磨具有相變合金之研磨對象物的研磨墊片,該研磨墊片之硬度之下限,以蕭氏硬度D計較佳為50。當墊片的蕭氏硬度D愈高時,墊片的機械性作用愈大,可提升研磨速度。此外,本發明實施形態之研磨用組成物係具有,即使為未含有研磨粒,亦可得到所謂的高研磨速度之優點。由如此般之觀點而言,蕭氏硬度D之又較佳的下限為60。
研磨具有相變合金之研磨對象物的研磨墊片,該研磨墊片之硬度之上限,以蕭氏硬度D計較佳為99。當墊片的蕭氏硬度D愈低時,愈不易使研磨對象物形成損傷。由如此般之觀點而言,蕭氏硬度D之更佳的上限為95。當墊片硬度未滿50時,墊片之機械性作用會變小,研磨速度會降低。尚,蕭氏硬度D,就定義上不會有100以上之值。墊片的蕭氏硬度D,可藉由蕭氏硬度D測定儀來測定。
蕭氏硬度D為50以上之研磨墊片,可由發泡體所形成,或是由布、不織布等之非發泡體所形成;作為研磨墊片之材質,可使用聚胺基甲酸酯、丙烯酸、聚酯、丙烯酸-酯共聚物、聚四氟乙烯、聚丙烯、聚乙烯、聚4-甲基戊烯、纖維素、纖維素酯、尼龍及醯胺等之聚醯胺、聚醯亞胺、聚醯亞胺醯胺、聚矽氧烷共聚物、環氧乙烷化合物、酚樹脂、聚苯乙烯、聚碳酸酯、環氧樹脂等之樹脂。
藉由本實施形態,可得到下列作用及效果。
係認為因以往的研磨用組成物中的添加劑(特別是錯化劑)等,使對於相變合金引起過度的蝕刻,其結果方面由於相變合金之氧化物會溶出,因而產生了凹坑。相較於此,分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物,係相變合金與化合物(其係分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物)之分子內的2個羰基會鍵結而形成不溶性的錯合物,因而於相變合金表面形成不溶性的脆性膜。其結果認為,抑制了因以往的研磨用組成物中的添加劑(特別是錯化劑)等之對於相變合金之過度蝕刻,而可抑制凹坑。
前述實施形態亦可變更如下。
‧前述實施形態之研磨用組成物,因應所需可進而含有界面活性劑或水溶性高分子、防腐劑般之一般所公知的添加劑。
‧前述實施形態之研磨用組成物,可為單液型或是以雙液型為首之多液型。
‧前述實施形態之研磨用組成物,可藉由以水來稀釋研磨用組成物之原液而調製出。
接著說明本發明之實施例及比較例。
藉由將表1中所記載的各成分進行混合,而調整出實施例1~24及比較例1~23之各組成物。表1中的“添加劑”欄之“種類”欄中,實施例時為表示各組成物中所包含的分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物之種類;比較例時為表示該分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物以外的添加劑之種類,或是表示由錯化劑(其係用來研磨以往含有金屬之表面的典型研磨用組成物中所含有者)等所選定的添加劑之種類。又,“含有量(質量%)”欄中為表示各組成物中該添加劑之含有量。同欄當中以“-”表示者,為未含有該添加劑之意。表1的“pH”欄中為表示各組成物中的pH。pH為添加無機酸或無機鹼,以調整成指定之值。
使用實施例1~24及比較例1~23之各組成物,並以表2所示之條件,來確認對於含有GST合金(Ge、Sb及Te的質量%比為2:2:5)之無圖型晶圓(blanket wafer)切片之蝕刻速度。關於以表2所示條件進行一定時間研磨時之研磨速度,係使用螢光X線分析法(XRF),藉由測定蝕刻試驗前後之膜厚差而算出。該結果為表示於表1中“評估”欄之“蝕刻速度”欄。尚,評估基準為對各組成物,與pH為相同的比較例1~3中任一項之組成物之蝕刻速度做比較,並將蝕刻速度為低之情形設為良好。
如表1中所示般,相較於使用未符合本發明條件之比較例1~23之組成物,使用實施例1~24之組成物時,在抑制蝕刻確認得到顯著優異之功效。
Claims (9)
- 一種研磨用組成物,其係使用於研磨具有相變合金之研磨對象物之用途之研磨用組成物,其特徵為包含選自於下述化合物之至少1種以上,前述化合物為分子內所含有的2個羰基為鍵結於分子內的第1位及第3位之碳原子的化合物。
- 如請求項1之研磨用組成物,其中前述化合物為下述一般式(1)所示的β-二酮化合物,
- 如請求項1之研磨用組成物,其中前述化合物為下述一般式(2)所示的β-酮醯胺化合物,
- 如請求項1之研磨用組成物,其中前述化合物為下述一般式(3)所示的β-酮酯化合物,
- 如請求項1~4中任一項之研磨用組成物,其係進而包含研磨粒。
- 如請求項5之研磨用組成物,其中前述研磨粒為膠體矽石。
- 如請求項1~4中任一項之研磨用組成物,其中前述相變合金為GST。
- 一種研磨方法,其特徵係使用請求項1~4中任一項之研磨用組成物來研磨具有相變合金之研磨對象物之表面。
- 一種基板之製造方法,其特徵係具有使用請求項1 ~4中任一項之研磨用組成物來研磨具有相變合金之研磨對象物之表面之步驟。
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JP2013247341A (ja) | 2013-12-09 |
KR20150020320A (ko) | 2015-02-25 |
WO2013179719A1 (ja) | 2013-12-05 |
TW201404874A (zh) | 2014-02-01 |
WO2013179721A1 (ja) | 2013-12-05 |
TW201350564A (zh) | 2013-12-16 |
US20150152290A1 (en) | 2015-06-04 |
KR102052015B1 (ko) | 2019-12-04 |
TW201402798A (zh) | 2014-01-16 |
WO2013179716A1 (ja) | 2013-12-05 |
TW201350565A (zh) | 2013-12-16 |
US9631121B2 (en) | 2017-04-25 |
WO2013179717A1 (ja) | 2013-12-05 |
WO2013179720A1 (ja) | 2013-12-05 |
TW201404873A (zh) | 2014-02-01 |
WO2013179718A1 (ja) | 2013-12-05 |
TWI557218B (zh) | 2016-11-11 |
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