TW201333129A - 研磨用組成物 - Google Patents
研磨用組成物 Download PDFInfo
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- TW201333129A TW201333129A TW101135839A TW101135839A TW201333129A TW 201333129 A TW201333129 A TW 201333129A TW 101135839 A TW101135839 A TW 101135839A TW 101135839 A TW101135839 A TW 101135839A TW 201333129 A TW201333129 A TW 201333129A
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- Prior art keywords
- polishing
- phase change
- polishing composition
- acid
- change alloy
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Abstract
本發明之研磨用組成物，為使用在對具有相變合金之研磨對象物進行研磨的用途之研磨用組成物，其特徵係含有離子性添加劑。離子性添加劑的例子，可列舉出陽離子性界面活性劑、陰離子性界面活性劑、雙性界面活性劑、及陽離子性水溶性高分子。
Description
本發明係關於適合於具有相變合金之研磨對象物的研磨之研磨用組成物。
PRAM(相變隨機存取記憶體)裝置(亦作為雙向記憶體裝置或PCRAM裝置而為人所知)中，係應用有可用於電子記憶用途中而在絕緣性非晶質相與傳導性結晶相之間進行電切換之相變材料(PCM)。適用於該用途之典型的相變材料的例子，可列舉出週期表的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種或複數種金屬元素之組合。特別有用之相變材料，為鍺(Ge)-銻(Sb)-碲(Te)合金(GST合金)。此等材料的物理狀態，係與加熱/冷卻速度、溫度、及時間相依而能夠可逆地變化。其他有用之相變合金的例子，係包含亞銻酸銦(InSb)。PRAM裝置中的記憶資訊，係藉由不同之物理相或狀態的傳導特性，以損失最小的方式來保存。
對半導體基材(例如積體電路)之含有金屬的表面進行研磨之方法，為人所知者有化學機械研磨(CMP：Chemical-mechanical Planarization)。CMP中所使用之研磨用組成物，典型而言，可含有研磨料、氧化劑及錯合劑並有效地應用蝕刻來研磨。
CMP，能夠用以製作出使用相變材料之記憶裝置而應用。然而，與由銅(Cu)或鎢(W)般的單一成分所構成之先前的金屬層不同，相變材料係以能夠使硫(S)、鈰(Ce)、鍺(Ge)、銻(Sb)、碲(Te)、銀(Ag)、銦(In)、錫(Sn)、鎵(Ga)等之複數種元素在結晶相及非晶質相之間可逆地變化之特定比率來混合。因此，較多之相變材料(例如GST)的物理性質，與PCM晶片中所應用之其他材料相比為軟質等，係與以往之金屬層材料的物理性質不同。因而難以將現行用以對含有金屬的表面進行研磨之研磨用組成物，直接應用在相變材料的研磨用途中。
此般狀況中，對於適合於具有相變合金之研磨對象物的研磨之研磨用組成物，乃進行各種探討。例如專利文獻1及2中，係揭示一種以含有研磨料、錯合劑、水及任意的氧化劑且具有相變合金之研磨對象物的研磨為目的之研磨用組成物。此等文獻中所揭示之研磨用組成物，係藉由改良用以對含有金屬的表面進行研磨時所使用之先前典型的研磨用組成物，來減少表面缺陷或相變材料的殘渣，但具有相變合金的蝕刻速率過高之問題。為了降低蝕刻速率，降低有利於蝕刻之氧化劑及錯合劑的濃度者乃為有效。惟當降低研磨用組成物中之氧化劑及錯合劑的濃度時，會產生研磨後的研磨對象物上所附著之研磨副產物或有機殘渣的量增加之新增課題。研磨副產物，係包含研磨時所產生之研磨屑。此外，有機殘渣，是指來自研磨墊
片、研磨裝置、洗淨刷或研磨用組成物之含有碳之雜質。本說明書中，亦將研磨副產物或有機殘渣總稱為「缺陷雜質」。
〔專利文獻1〕日本特表2010-534934號公報
〔專利文獻2〕日本特開2009-525615號公報
因此，本發明之目的在於提供一種可適合地使用在對具有相變合金之研磨對象物進行研磨的用途之研磨用組成物，尤其提供一種可防止研磨副產物或有機殘渣的產生之研磨用組成物。
為了達成上述目的，本發明之一型態中，係提供一種研磨用組成物，為使用在對具有GST合金等的相變合金之研磨對象物進行研磨的用途之研磨用組成物，其特徵為：含有離子性添加劑。
一實施型態中，前述離子性添加劑為選自陽離子性界面活性劑、陰離子性界面活性劑及雙性界面活性劑之1種以上。
前述離子性添加劑較佳為陽離子性水溶性高分子。
研磨用組成物中之離子性添加劑的濃度較佳為0.0001~10質量%。
本發明之其他型態中，係提供一種研磨方法，其特徵為：使用前述型態之研磨用組成物，對具有相變合金之研磨對象物的表面進行研磨。
本發明之另外型態中，係提供一種相變裝置的製造方法，其特徵為包含：使用上述型態之研磨用組成物，對具有相變合金之研磨對象物的表面進行研磨之步驟。
根據本發明，係提供一種可適合地使用在對具有相變合金之研磨對象物進行研磨的用途之研磨用組成物，尤其提供一種可有效減少研磨副產物或有機殘渣之研磨用組成物。
以下係說明本發明之一實施形態。
本發明之研磨用組成物，係使用在對具有相變合金之研磨對象物進行研磨的用途，詳細而言，係使用在藉由對具有相變合金之研磨對象物的表面進行研磨而製造相變裝置之用途。相變合金，在PRAM(相變隨機存取記憶體)裝置(亦作為雙向記憶體裝置或PCRAM裝置而為人所知)中，係應用作為可用於電子記憶用途中而在絕緣性非晶質相與傳導性結晶相之間進行電切換之材料。適用於該
用途之相變合金的例子，可列舉出週期表的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種或複數種金屬元素之組合。特別有用之相變材料，為鍺(Ge)-銻(Sb)-碲(Te)合金(GST合金)。
本實施形態之研磨用組成物，可含有離子性添加劑。離子性添加劑，是指在水溶液中具有正或負的電位之物質，並可改變研磨對象物或缺陷雜質的電位，詳細而言為動電勢之物質。離子性添加劑，藉由鍵結或吸附於相變合金及缺陷雜質的兩方或單方的表面，將相變合金表面及缺陷雜質表面的電荷調整為同種(亦即正彼此或負彼此)，使排斥力作用於相變合金表面及缺陷雜質表面之間。亦即，雖然詳細機制仍未明瞭，但可考量為下列3種中的任一種作用。
(1)鍵結或吸附於相變合金表面及缺陷雜質表面兩者，並將排斥力賦予至相變合金表面及缺陷雜質表面之間。
(2)主要鍵結或吸附於相變合金表面，並將排斥力賦予至與缺陷雜質所具有之原先的電荷之間。
(3)主要鍵結或吸附於缺陷雜質，並將排斥力賦予至與相變合金所具有之原先的電荷之間。
在選擇吸附或附著於相變合金表面之離子性添加劑
時，較佳係考量到構成相變合金之金屬的種類與含量。亦即，較佳係選擇：在構成相變合金之金屬中，對含量多之金屬的每單位面積所賦予之電荷量，較對含量少之金屬的每單位面積所賦予之電荷量更多之離子性添加劑。例如在Ge、Sb及Te的質量為2：2：5的GST合金時，較佳係選擇：對含量多之Te的每單位面積所賦予之電荷量，較對含量少之Ge及Sb的每單位面積所賦予之電荷量更多之離子性添加劑。
在選擇吸附或附著於缺陷雜質表面之離子性添加劑時，較佳係考量到缺陷雜質的成分。例如，來自聚胺甲酸酯製的研磨墊片之有機殘渣，在pH3.0附近具有正電荷。此外，來自聚乙烯醇製的洗淨刷之有機殘渣，在pH3.0附近具有負電荷。在得知作為缺陷雜質之有機殘渣的成分時，當選擇具有相對於各有機殘渣的電荷為相反電荷之離子性添加劑來使用時，可在離子性添加劑與有機殘渣之間產生引力，亦即可有效率地將電荷賦予至有機殘渣表面。再者，當缺陷雜質為研磨副產物時，較佳如前述般地考量到構成相變合金之金屬的種類與含量。
離子性添加劑為具有電荷之化合物，具體可列舉出陽離子性界面活性劑、陰離子性界面活性劑、雙性界面活性劑以及具有電荷之水溶性高分子。陽離子性界面活性劑，有四級銨鹽型、烷基胺鹽型、及吡啶環化合物型等，具體可列舉出四甲基銨鹽、四丁基銨鹽、十二烷基二甲基苄基銨鹽、烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲
基銨鹽、單烷基胺鹽、二烷基胺鹽、三烷基胺鹽、脂肪酸醯胺-胺及烷基吡啶鹽。陰離子性界面活性劑，有羧酸型、磺酸型、硫酸酯型及磷酸酯型等，具體可列舉出椰油脂肪酸肌胺酸三乙醇胺、椰油脂肪酸甲基牛磺酸鹽脂肪族單羧酸鹽、烷基苯磺酸鹽、烷磺酸鹽、α-烯烴磺酸鹽、聚氧乙烯烷基醚硫酸鹽、烷基硫酸鹽、聚氧乙烯烷基醚磷酸鹽、烷基磷酸鹽等。雙性界面活性劑的例子，可列舉出烷基三甲甘胺酸及氧化烷基胺。具有陽離子電荷之水溶性高分子，具體可列舉出甲殼素、經陽離子改質之羥乙基纖維素等之多醣體、聚伸烷亞胺、聚伸烷聚胺、聚乙烯胺、聚胺-表氯醇縮合物、陽離子性聚丙烯醯胺、聚二烯丙基二甲基銨鹽及二烯丙基胺鹽-丙烯醯胺聚合物等。具有陰離子電荷之水溶性高分子，具體可列舉出聚丙烯酸鹽、苯乙烯-馬來酸共聚物的銨鹽等。所賦予之電荷的絕對值愈大，作用於相變合金表面及缺陷雜質表面之間之排斥力愈大。此外，較佳係從不會對研磨及蝕刻造成影響，且對相變合金及缺陷雜質之化學或物理吸附力高之觀點來選擇。從該觀點來看，當相變合金表面及缺陷雜質表面具有負電荷時，較佳為具有較多極性基之陽離子性水溶性高分子，當中尤佳為聚伸烷聚胺。此外，當相變合金表面及缺陷雜質表面具有正電荷時，較佳為陰離子性界面活性劑或陰離子性水溶性高分子，當中尤佳為聚氧乙烯十二烷基醚磷酸酯。
離子性添加劑的分子量，較佳為10萬以下，尤佳為1
萬以下。隨著離子性添加劑的分子量變小，相變合金及缺陷雜質的表面上之離子性添加劑的立體阻礙變少。其結果可有效率地賦予電荷，且排斥力容易作用，所以可有效地減少缺陷雜質。
研磨用組成物中之離子性添加劑的含量較佳為0.001質量%以上，尤佳為001質量%以上。隨著離子性添加劑的含量增多，離子性添加劑鍵結或吸附於相變合金表面及缺陷雜質的表面之機率提高。其結果可有效率地賦予電荷，且排斥力容易作用，所以可有效地減少缺陷雜質。
研磨用組成物可含有研磨料。研磨料可為無機粒子、有機粒子、及有機無機複合粒子中的任一種。無機粒子的具體例，例如可列舉出由二氧化矽、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。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。當中較佳為二氧化矽粒子，特佳為膠體二氧化矽。
研磨料可經表面改質。一般的膠體二氧化矽，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，二氧化矽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料，在酸性條件下亦可彼此強力相斥而良好地分散，其結果可提升研磨用組成物的保存穩定
性。此般經表面改質之研磨料，例如可將鋁、鈦或鋯等之金屬或此等的氧化物與研磨料混合以摻雜於研磨料的表面而得。或者是使用具有胺基之矽烷偶合劑，以磺酸或膦酸對研磨料的表面進行改質。
不論在何種情形，當添加研磨料時，離子性添加劑所具有之電位與研磨料所具有之電位，較佳為同號。當離子性添加劑所具有之電位與研磨料所具有之電位為異號時，會有研磨料經由離子性添加劑而凝聚之疑慮。
研磨用組成物中之研磨料的含量，較佳為0.01質量%以上，尤佳為0.05質量%以上，更佳為0.1質量%以上。隨著研磨料的含量增多，乃具有可提升研磨用組成物去除相變合金之速度之優點。
此外，研磨用組成物中之研磨料的含量，較佳為20質量%以下，尤佳為15質量%以下，更佳為10質量%以下。隨著研磨料的含量減少，可抑制研磨用組成物的材料成本，並且不易引起研磨料的凝聚。此外，藉由使用研磨用組成物來研磨相變合金，可容易得到表面缺陷少之研磨面。
研磨料的平均一次粒徑，較佳為5nm以上，尤佳為7nm以上，更佳為10nm以上。隨著研磨料的平均一次粒徑增大，乃有利於提升研磨用組成物去除相變合金之速度。研磨料的平均一次粒徑之值，例如可根據由BET法所測定之研磨料的比表面積來計算。
此外，研磨料的平均一次粒徑，較佳為100nm以下，
尤佳為90nm以下，更佳為80nm以下。隨著研磨料的平均一次粒徑減少，可藉由使用研磨用組成物來研磨相變合金而容易得到表面缺陷少之研磨面。
研磨料的平均二次粒徑，較佳為150nm以下，尤佳為120nm以下，更佳為100nm以下。研磨料的平均二次粒徑之值，例如可藉由雷射光散射法來測定。
研磨料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料的平均聚集度，較佳為1.2以上，尤佳為1.5以上。隨著研磨料的平均聚集度增大，乃具有可提升研磨用組成物去除相變合金之速度之優點。
此外，研磨料的平均聚集度，較佳為4以下，尤佳為3以下，更佳為2以下。隨著研磨料的平均聚集度降低，藉由使用研磨用組成物來研磨相變合金，可容易得到表面缺陷少之研磨面。
研磨用組成物的pH，較佳為7以下，尤佳為5以下，更佳為3以下。隨著研磨用組成物的pH變小，乃不易因研磨用組成物而引起相變合金的蝕刻，其結果更可抑制表面缺陷的產生。
將研磨用組成物的pH調整為期望的值時，可使用pH調整劑。所使用之pH調整劑，可為酸或鹼，此外亦可為無機及有機化合物中的任一種。
研磨用組成物可含有氧化劑。氧化劑係具有將研磨對象物的表面氧化之作用。當將氧化劑添加於研磨用組成物時，乃具有提升研磨用組成物研磨相變合金之速度之效果。然而，當使用用以對含有金屬的表面進行研磨所使用之先前典型的研磨用組成物來研磨相變合金時，相變合金容易被過度研磨。此可考量為相變合金的特性與銅般之一般半導體裝置中所使用之金屬材料的特性不同之故。
研磨用組成物中之氧化劑的含量，較佳為0.1質量%以上，尤佳為0.3質量%以上。隨著氧化劑的含量增多，可抑制有機殘渣的產生。
研磨用組成物中之氧化劑的含量，較佳為10質量%以下，尤佳為5質量%以下。隨著氧化劑的含量減少，不易引起氧化劑對相變合金所造成的過剩氧化，而抑制相變合金的過剩研磨。
能夠使用之氧化劑，例如有過氧化物。過氧化物的具體例，例如可列舉出過氧化氫、過乙酸、過碳酸鹽、過氧化脲及過氫氯酸、以及過硫酸鈉、過硫酸鉀及過硫酸銨等之過硫酸鹽。當中就研磨速度之觀點來看，較佳為過硫酸鹽及過氧化氫，就水溶液中的穩定性及對環境負荷之觀點來看，特佳為過氧化氫。
研磨用組成物可含有錯合劑。錯合劑係具有將相變合
金的表面化學蝕刻之作用，而具有提升研磨用組成物研磨相變合金之速度之功用。然而，當使用用以對含有金屬的表面進行研磨所使用之先前典型的研磨用組成物來研磨相變合金時，會引起相變合金的過度研磨，其結果為，相變合金容易被過度研磨。此可考量為相變合金的特性與銅般之一般半導體裝置中所使用之金屬材料的特性不同之故。
研磨用組成物中之錯合劑的含量，較佳為0.01質量%以上，尤佳為0.1質量%以上。隨著錯合劑的含量增多，可增加錯合劑對相變合金所進行之蝕刻效果，故有助於提升研磨用組成物研磨相變合金之速度。
研磨用組成物中之錯合劑的含量，較佳為10質量%以下，尤佳為1質量%以下。隨著錯合劑的含量減少，不易引起錯合劑對相變合金所造成的過剩蝕刻，而抑制相變合金的過剩研磨。
能夠使用之錯合劑，例如可列舉出無機酸、有機酸、及胺基酸。無機酸的具體例，例如可列舉出硫酸、硝酸、硼酸、碳酸、次磷酸、亞磷酸及磷酸。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、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基庚酸、苯甲酸、二醇酸、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、乙烷磺酸及羥乙基磺酸等之有機硫酸。此外，亦可使用無機酸或有機
酸的銨鹽或鹼金屬鹽等之鹽，來取代無機酸或有機酸、或是與無機酸或有機酸組合使用。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、二羥乙甘胺酸、N,N-雙(2-羥乙基)甘胺酸、三(羥甲基)甲甘胺酸、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、半胱胺酸、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、重氮絲氨酸、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、色胺酸及亞胺基二乙酸。當中就研磨速度的提升之觀點來看，錯合劑較佳為甘胺酸、丙胺酸、亞胺基二乙酸、蘋果酸、酒石酸、檸檬酸、二醇酸、羥乙基磺酸或是此等之銨鹽或鹼金屬鹽。
研磨用組成物可含有金屬防蝕劑。當將金屬防蝕劑添加於研磨用組成物時，乃具有在使用研磨用組成物進行研磨後之相變合金上更不易產生凹陷等表面缺陷之效果。此外，金屬防蝕劑，當研磨用組成物中含有氧化劑及/或錯合劑時，可緩和氧化劑對相變合金表面所造成的氧化，並
且發揮與因氧化劑對相變合金表面金屬所造成的氧化所產生之金屬離子反應，而生成不溶性的錯合物之功用。其結果可抑制錯合劑對相變合金所進行之蝕刻，而抑制相變合金的過度研磨。
能夠使用之金屬防蝕劑的種類並無特別限定，較佳為雜環型化合物。雜環型化合物中之雜環的員數並無特別限定。此外，雜環型化合物可為單環化合物，或是具有縮合環之多環化合物。
作為金屬防蝕劑之雜環型化合物的具體例，例如可列舉出吡咯化合物、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、氮茚化合物、吲嗪化合物、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、布替利嗪化合物、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。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。咪唑化合物的具體例，例如可列舉出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。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。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。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。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，而抑制相變合金的過剩研磨。
研磨用組成物中之金屬防蝕劑的含量，較佳為0.001質量%以上，尤佳為0.01質量%以上，更佳為0.1質量%以上。隨著金屬防蝕劑的含量增多，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，而抑制相變合
金的過剩研磨。
此外，研磨用組成物中之金屬防蝕劑的含量，較佳為10質量%以下，尤佳為5質量%以下，更佳為1質量%以下。隨著金屬防蝕劑的含量減少，乃具有提升研磨用組成物研磨相變合金之速度之效果。
根據本實施形態，可得到下列作用及效果。
本實施形態之研磨用組成物中所含有之離子性添加劑，藉由鍵結或吸附於研磨對象物中所包含之相變合金及缺陷雜質的兩方或單方的表面，將相變合金表面及缺陷雜質表面的電位調整為同種(正與正或負與負)，使排斥力作用於相變合金表面及缺陷雜質表面之間。因此，本實施形態之研磨用組成物，在具有相變合金之研磨對象物的研磨中，於研磨前或研磨時，可抑制由研磨裝置環境及研磨用組成物所產生之缺陷雜質堆積及殘留於研磨對象物上。
前述實施形態可變更如下。
．前述實施形態之研磨用組成物，可含有兩種以上的離子性添加劑。此時，全部離子性添加劑不需具有同種類的電位，只需使研磨對象物中的相變合金與缺陷雜質的表面帶有同種類的電位即可。
．前述實施形態之研磨用組成物，可因應必要，進一步含有未被分類為離子性添加劑之界面活性劑或水溶性高分子、防腐劑般之一般所知的添加劑。
．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的原液而調製出。
接著說明本發明之實施例及比較例。
將膠體二氧化矽及離子性添加劑混合於水，添加無機酸作為pH調整劑並將pH值調整為大約3.0，藉此調製出實施例1~27及比較例3~6之研磨用組成物。將膠體二氧化矽混合於水，添加無機酸作為pH調整劑並將pH值調整為大約3.0，藉此調製出不含離子性添加劑之比較例1之研磨用組成物。將膠體二氧化矽及氧化劑混合於水，添加無機酸作為pH調整劑並將pH值調整為大約3.0，藉此調製出比較例2之研磨用組成物。各研磨用組成物中之離子性添加劑的詳細內容如第1表所示。雖然於第1表中未顯示，但實施例1~27及比較例1~6之研磨用組成物中的膠體二氧化矽，均具有35nm的平均一次粒徑及約70nm的平均二次粒徑(平均聚集度2)，此等研磨用組成物中之膠體二氧化矽的含量為0.5質量%。此外，比較例2之研磨用組成物，係含有作為氧化劑的過氧化氫0.3質量%。
關於實施例1~27及比較例1~6之各研磨用組成物中所使用之離子性添加劑，係以第2表所示之方法及條件，來測定藉由該離子性添加劑(濃度0.1質量%、pH約3.0)水溶液進行處理後之Ge、Sb及Te之各金屬表面的電荷。該結果分別顯示於第4表之“動電勢”欄的“Ge”、“Sb”及“Te”欄。
此外，使用實施例1~27及比較例1~6之各研磨用組成物，並以第3表所示之條件來研磨含有GST合金(Ge、Sb及Te的質量比為2：2：5)之原晶圓。
確認研磨後之各晶圓上的研磨副產物及有機殘渣。研磨副產物及有機殘渣的確認，係使用缺陷檢查裝置來測定研磨後之各晶圓上的全部缺陷，並使用掃描型電子顯微鏡(SEM)特定出其中的研磨副產物及有機殘渣，然後予以計數來進行。該結果顯示於第4表的“評估”欄之“研磨副產物”及“有機殘渣”欄。本評估結果中，以研磨副產物及有機殘渣各自的個數為500個以下者為“◎”，以501~1000個者為“○”，以1001~10000個者為“△”，以多於10000個者為“×”。
從依據直流四探針法所進行之薄片電阻的測定中，求取以第3表所示之條件研磨既定時間後之各晶圓的厚度與研磨前之晶圓的厚度，並以研磨時間除上該差來算出研磨速度。以所算出之研磨速度之值為1000Å/min以下者為“○”，以高於1000且為2000Å/min以下者為“△”，以高於2000Å/min者為“×”，並顯示於第4表的“評估”欄之“研
磨速度”欄。
如第4表所示，使用實施例1~27之研磨用組成物時，與使用不含離子性添加劑之比較例1~6之研磨用組成物時相比，可觀察到研磨副產物或有機殘渣顯著地減少。
Claims (7)
- 一種研磨用組成物，為使用在對具有相變合金之研磨對象物進行研磨的用途之研磨用組成物，其特徵為：含有離子性添加劑。
- 如申請專利範圍第1項之研磨用組成物，其中離子性添加劑，為選自陽離子性界面活性劑、陰離子性界面活性劑及雙性界面活性劑之1種以上。
- 如申請專利範圍第1項之研磨用組成物，其中離子性添加劑為陽離子性水溶性高分子。
- 如申請專利範圍第1至3項中任一項之研磨用組成物，其中研磨用組成物中之離子性添加劑的濃度為0.0001~10質量%。
- 如申請專利範圍第1至3項中任一項之研磨用組成物，其中前述相變合金為鍺-銻-碲合金。
- 一種研磨方法，其特徵為：使用如申請專利範圍第1至3項中任一項之研磨用組成物，對具有相變合金之研磨對象物的表面進行研磨。
- 一種相變裝置的製造方法，其特徵為包含：使用如申請專利範圍第1至3項中任一項之研磨用組成物，對具有相變合金之研磨對象物的表面進行研磨之步驟。
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| EP2997104A4 (en) * | 2013-05-15 | 2017-01-25 | Basf Se | Use of a chemical-mechanical polishing (cmp) composition for polishing a substrate or layer containing at least one iii-v material |
| BR102014003807A2 (pt) * | 2014-02-18 | 2014-09-09 | Demoiselle Ind E Com De Prod Para Revitalizacao Ltda | Composição para limpeza, proteção e revitalização de superfícies em geral e produto assim obtido |
| CN104002252B (zh) * | 2014-05-21 | 2016-06-01 | 华侨大学 | 超细磨料生物高分子柔性抛光膜及其制备方法 |
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| CN106574171B (zh) * | 2014-08-22 | 2019-03-19 | 嘉柏微电子材料股份公司 | 锗的化学机械抛光 |
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