TWI780075B - 化學機械研磨液及其應用 - Google Patents
化學機械研磨液及其應用 Download PDFInfo
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- TWI780075B TWI780075B TW106133680A TW106133680A TWI780075B TW I780075 B TWI780075 B TW I780075B TW 106133680 A TW106133680 A TW 106133680A TW 106133680 A TW106133680 A TW 106133680A TW I780075 B TWI780075 B TW I780075B
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- Prior art keywords
- mechanical polishing
- chemical mechanical
- copper
- polishing fluid
- acid
- Prior art date
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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
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Abstract
本發明一方面提供了一種化學機械研磨液，其包含研磨顆粒、腐蝕抑制劑、錯合劑、氧化劑、以及至少含有一種磺酸鹽類陰離子表面活性劑。本發明另一方面提供該研磨液在金屬銅研磨中的應用。本發明實現了提高研磨液對銅與鉭阻擋層的研磨選擇比的功效。本發明用於晶圓的研磨可改善研磨後銅線的碟型凹陷(Dishing)和介質層侵蝕(Erosion)，且研磨後晶圓無銅殘留物以及腐蝕等缺陷。
Description
本發明有關於化學機械研磨領域，尤指一種化學機械研磨液及其在研磨金屬銅中的應用。
隨著半導體技術的發展，電子部件的微小化，一個積體電路中包含了數以百萬計的電晶體。在運行過程中，在整合了如此龐大數量的能迅速開關的電晶體，傳統的鋁或是鋁合金內連線，使得信號傳遞速度降低，而且電流傳遞過程中需要消耗大量能源，在一定意義上，也阻礙了半導體技術的發展。為了進一步發展，人們開始尋找採用擁有更高電學性質的材料取代鋁的使用。眾所周知，銅的電阻小，擁有良好的導電性，這加快了電路中電晶體間信號的傳遞速度，還可提供更小的寄生電容能力，較小電路對於電遷移的敏感性。這些電學優點都使得銅在半導體技術發展中擁有良好的發展前景。 但在銅的積體電路製造過程中發現，銅會遷移或擴散進入到積體電路的電晶體區域，從而對於半導體的電晶體的性能產生不利影響，因而銅的內連線只能以鑲嵌製程製造，即：在第一層裡形成溝槽、在溝槽內填充銅阻擋層和銅、形成金屬導線並覆蓋在介電層上。然後通過化學機械研磨將介電層上多餘的銅/銅阻擋層除去，在溝槽裡留下單個內連線。銅的化學機械研磨過程一般分為3個步驟，第1步是先用較高的下壓力，以快速且高效的移除率除去基底表面上大量的銅並留下一定厚度的銅，第2步用較低的移除率去除剩餘的金屬銅並停在阻擋層，第3步再用阻擋層研磨液去除阻擋層及部分介電層和金屬銅，實現平坦化。 銅研磨一方面要儘快去除阻擋層上多餘的銅，另一方面要儘量減小研磨後銅線的碟型凹陷。在銅研磨前，金屬層在銅線上方有部分凹陷。研磨時，介質材料上的銅在主體壓力下(較高)易於被去除，而凹陷處的銅所受的研磨壓力比主體壓力低，銅移除率小。隨著研磨的進行，銅的高度差會逐漸減小，達到平坦化。但是在研磨過程中，如果銅研磨液的化學作用太強，靜態腐蝕速率太高，則銅的鈍化膜即使在較低壓力下(如銅線凹陷處)也易於被去除，導致平坦化效率降低，研磨後的碟型凹陷增大。 隨著積體電路的發展，一方面，在傳統的IC行業中，為了提高積集度、降低能耗、縮短延遲時間，線寬越來越窄，介質層使用機械強度較低的低介電(low-k)材料，佈線的層數也越來越多，為了保證積體電路的性能和穩定性，對銅化學機械研磨的要求也越來越高。要求在保證銅的移除率的情況下降低研磨壓力，提高銅線表面的平坦化，控制表面缺陷。另一方面，由於物理局限性，線寬不能無限縮小，半導體行業不再單純地依賴在單一晶圓上整合更多的器件來提高性能，而轉向於多晶片封裝。矽通孔(TSV)技術作為一種通過在晶片和晶片之間、晶圓與晶圓之間製作垂直導通，實現晶片之間互連的最新技術而得到工業界的廣泛認可。TSV能夠使晶片在三維方向堆疊的密度最大，外形尺寸最小，大大改善晶片速度和低功耗的性能。 目前的TSV製程是結合傳統的IC製程形成貫穿矽基底的銅穿孔，即在TSV開口中填充銅實現導通，填充後多餘的銅也需要利用化學機械研磨去除達到平坦化。與傳統IC工業不同，由於矽通孔很深，填充後表面多餘的銅通常有幾到幾十微米厚。為了快速去除這些多餘的銅。通常需要具有很高的銅移除率，同時研磨後的表面平整度好。為了使銅在半導體技術中更好的應用，人們不斷嘗試新的研磨液的改進。 中國專利CN1256765C提供了一種含有檸檬酸、檸檬酸鉀組成的螯合有機酸緩衝體系的研磨液。CN1195896C採用含有氧化劑、羧酸鹽如檸檬酸銨、磨料漿液、一種任選的三唑或三唑衍生物的研磨液。CN1459480A提供了一種銅的化學機械研磨液，其包含了成膜劑和成膜助劑：成膜劑由強鹼和醋酸混合組成的緩衝溶液構成，成膜助劑為硝酸鉀(鈉)鹽。美國專利US552742提供了一種金屬化學機械研磨漿料，包括一種含有芳綸矽氧、烷聚矽氧烷、聚氧化烯醚及其共聚物的表面活性劑。US6821897B2提供了一種採用含有聚合物錯合劑的研磨劑的銅化學機械研磨方法，其採用含負電荷的聚合物，其中包括硫磺酸及其鹽、硫酸鹽、磷酸、磷酸鹽、磷酸酯等。而US5527423金屬化學機械研磨漿料，包括一種表面活性劑：芳綸矽氧烷、聚矽氧烷、聚氧化烯醚及其共聚物。中國專利CN1334961A提供了一種含有氧化金屬溶解劑、保護膜形成劑和該保護膜形成劑的溶解助劑的金屬研磨液，其中，保護劑形成劑的溶解助劑為多羧酸鹽類、乙烯基聚合物、磺酸、磺酸鹽及醯胺等表面活性劑的一種或多種。該溶解助劑用來提高保護膜形成劑的溶解度性能。中國專利CN101418187A中提供了一種研磨液，其中添加陽離子表面活性劑(聚乙烯亞胺)、季銨鹽型表面活性劑(十六烷基三甲基氯化銨)和非離子型表面活性劑(聚乙二醇)，可以降低阻擋層鉭/氮化鉭(Ta/TaN)的去除速率。
本發明則旨在提出一種化學機械研磨液，通過在研磨液中添加不含苯環的氮唑類腐蝕抑制劑和磺酸鹽類陰離子表面活性劑的組合，維持了銅的高去除速率，降低了鉭阻擋層的去除速率，從而實現在提高研磨液對銅與鉭阻擋層的研磨選擇比的同時，改善研磨後銅線的碟型凹陷(Dishing)和介質層侵蝕(Erosion)，且研磨後無銅殘留和腐蝕等缺陷。 具體地，本發明一方面係提供一種化學機械研磨液，其包含有研磨顆粒、腐蝕抑制劑、錯合劑、氧化劑、以及至少一種磺酸鹽類陰離子表面活性劑。 其中，該磺酸鹽類陰離子表面活性劑為烷基磺酸鹽、烷基芳基磺酸鹽。 較佳地，該烷基磺酸鹽為C10~C18的烷基磺酸鹽，該烷基芳基磺酸鹽為含有C12~C18的烷基苯磺酸鹽，聚合度為200~600的聚苯乙烯磺酸鹽、4-乙烯基苯磺酸鹽和亞甲基二萘磺酸鹽，該鹽為鉀鹽和鈉鹽。 較佳地，該磺酸類陰離子表面活性劑含量為0.001 ~ 0.5wt%；更佳地，該磺酸類陰離子表面活性劑含量為0.005 ~ 0.1wt%。 較佳地，該研磨顆粒為二氧化矽溶膠。 較佳地，該研磨顆粒的粒徑為20~150nm；更佳地，該研磨顆粒的粒徑為50~120nm。 較佳地，該研磨顆粒的濃度為0.05~2wt%。更佳地，該研磨顆粒的濃度為0.1~1 wt %。 較佳地，該錯合劑為氨羧化合物及其鹽。更佳地，該氨羧化合物及其鹽為甘氨酸、丙氨酸、纈氨酸、亮氨酸、脯氨酸、苯丙氨酸、酪氨酸、色氨酸、賴氨酸、精氨酸、組氨酸、絲氨酸、天冬氨酸、谷氨酸、天冬醯胺、穀氨醯胺、氨三乙酸、乙二胺四乙酸、環己二胺四乙酸、乙二胺二琥珀酸、二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一種或多種。 較佳地，該錯合劑的濃度為0.1～5wt%；更佳地，該錯合劑的濃度為0.5～3wt%。 較佳地，該腐蝕抑制劑為不含苯環的氮唑類化合物中的一種或多種。具體為：1，2，4-三氮唑、3-氨基-1，2，4-三氮唑、4-氨基-1，2，4-三氮唑、3，5-二氨基-1，2，4-三氮唑、5-羧基-3-氨基-1，2，4-三氮唑、3-氨基-5-巰基-1，2，4-三氮唑、5-乙酸-1H-四氮唑、5-甲基四氮唑和5-氨基-1H-四氮唑中的一種或多種。 較佳地，該腐蝕抑制劑濃度為0.001～2wt%；更佳地，該腐蝕抑制劑濃度為0.005～1wt%。 較佳地，該氧化劑為過氧化氫。 較佳地，該氧化劑的濃度為0.05～5wt%；更佳地，該氧化劑的濃度為0.1～3wt%。 較佳地，該化學機械研磨液的pH為5~8。 另外，該研磨液中還包括pH調節劑、粘度調節劑、消泡劑。 並且，該研磨液可以濃縮配製，在使用時用去離子水進行稀釋並添加氧化劑至本發明的濃度範圍使用。 本發明的另一方面，係提供一種上述的化學機械研磨液在金屬銅的研磨中的應用。 與現有技術相比較，本發明的優勢在於： 1)本發明在研磨液中添加不含苯環的氮唑類腐蝕抑制劑和磺酸鹽類陰離子表面活性劑的組合，維持了銅的高移除率，降低了鉭阻擋層的移除率，實現了提高研磨液對銅與鉭阻擋層的研磨選擇比的功效； 2)本發明用於晶圓的研磨可改善研磨後銅線的碟型凹陷(Dishing)和介質層侵蝕(Erosion)，且研磨後晶圓係無銅殘留物以及腐蝕等缺陷。
以下係藉由實施例的方式進一步說明本發明，但並不以此將本發明限制在該的實施例範圍之中。
實施例 1~27表1係提供本發明的化學機械研磨液的實施例1~27，按表中所給配方，將除了氧化劑以外的其他組分混合均勻，用水補足重量百分比至100%。用氫氧化鉀(KOH)或硝酸(HNO
3)調節到所需要的pH值。使用前加入氧化劑，混合均勻即可。 表1實施例1~27
效果實施例表2係提供本發明的化學機械研磨液的實施例28~37及對照組實施例1~4，按表中所給配方，將除了氧化劑以外的其他組分混合均勻，用水補足重量百分比至100%。用KOH或HNO
3調節到所需要的pH值。使用前加入氧化劑，混合均勻即可，得到具體實施例如下。 表2：對照例1~4及實施例28~37
採用對照組研磨液和本發明的研磨液28~37按照下述條件對空片銅(Cu)、鉭(Ta)進行研磨。具體研磨條件：壓力1.5psi和/或2.0psi；研磨盤及研磨頭轉速73/67rpm，研磨墊IC1010，研磨液流速350ml/min，研磨機台為12” Reflexion LK，研磨時間為1分鐘(min)。 採用對照組研磨液和本發明的研磨液按照下述條件對含圖案的銅晶圓進行研磨。研磨條件：研磨盤及研磨頭轉速73/67rpm，研磨墊IC1010，研磨液流速350ml/min，研磨機台為12” Reflexion LK。在研磨盤1上用2psi的下壓力研磨有圖案的銅晶圓至殘留銅約3000A，然後再在研磨盤2上用1.5psi 的下壓力將殘留的銅去除。用XE-300P 原子力顯微鏡測量有圖案的銅晶圓上5um/1um(銅線/介電材料線寬)的銅線陣列區的碟型凹陷值(Dishing)和介質層侵蝕(Erosion)，結果如表3： 表3：對照組研磨液1~4和本發明研磨液28~37的研磨效果
從表3中可以看出：與對比例1相比，本發明的在研磨液中加入了含有磺酸鹽類陰離子表面活性劑，能在維持較高的銅移除率的同時，降低鉭的移除率，大大提高了Cu/Ta移除選擇比，因此有效地降低了圖案晶圓研磨後的碟型凹陷值和介質層侵蝕值，而對照組1即使加入了較多的腐蝕抑制劑，也不能有效地抑制鉭的移除率，導致碟形凹陷和介質層侵蝕值均較高。 進一步參閱圖1及圖2，其分別為使用對照組1及實施例28研磨後的銅圖案晶圓中銅線寬為5微米，介電材料寬為1微米的密線陣列區表面形貌圖。從圖中可以看出，使用對照組1作為研磨液，研磨後的銅線存在89.2奈米(nanometer，nm)的碟型凹陷和57.5nm的介質層侵蝕；而使用本實施例28作為研磨液，研磨後的銅線碟型凹陷減低至25nm，介質層侵蝕降至4.2nm，本發明的研磨液對研磨後的表面形貌特別是介質層的侵蝕的減低效果非常顯著。同時，結合實施例28與對照組2的組分比較可發現，選擇帶有苯環的唑類腐蝕抑制劑苯並三氮唑和磺酸鹽類陰離子表面活性劑的組合，雖然能降低鉭的移除率，但大大抑制了銅的移除率，無法有效地去除銅。與本發明實施例28相比，對照組3和4加入採用了不帶苯環的唑類腐蝕抑制劑和磺酸鹽類陰離子表面活性劑的組合，但對比例3的pH值過低，銅和鉭的移除率也較高，導致碟型凹陷和介質層侵蝕均較大。而對照組4的pH值過高，導致銅的移除率大大降低，無法有效去除銅。 綜上所述，本發明在研磨液中添加不含苯環的氮唑類腐蝕抑制劑和磺酸鹽類陰離子表面活性劑的組合，維持了銅的高移除率，降低了鉭阻擋層的移除率，實現了提高研磨液對銅與鉭阻擋層的研磨選擇比的功效；本發明用於晶圓的研磨可改善研磨後銅線的碟型凹陷(Dishing)和介質層侵蝕(Erosion)，且研磨後晶圓無銅殘留物以及腐蝕等缺陷。 以上對本發明的具體實施例進行了詳細描述，但其只是作為範例，本發明並不限制於以上描述的具體實施例。對於本領域技術人員而言，任何對本發明進行的等同修改和替代也都在本發明的範疇之中。因此，在不脫離本發明的精神和範圍下所作的均等變換和修改，都應涵蓋在本發明的範圍內。 上述內容概述了若干實施例之特徵以使得熟習此項技術者可更好理解本揭示之各態樣。熟習此項技術者應瞭解，其可易於將本揭示用作設計或修改用於進行與本文中介紹之實施例相同的目的及/或實現與其相同的優勢之其他程序及結構之基礎。熟習此項技術者亦應認識到，此類等效結構並不脫離本揭示之精神及範疇，並且在不脫離本揭示之精神及範疇的情況下可在此處進行各種改變、替代及更改。
圖1為使用對照組1研磨後的銅圖案晶圓中銅線寬為5微米，介電材料寬為1微米的密線陣列區表面形貌圖； 圖2為使用實施例28研磨後的銅圖案晶圓中銅線寬為5微米，介電材料寬為1微米的密線陣列區表面形貌圖。
Claims (23)
- 一種化學機械研磨液，由研磨顆粒、腐蝕抑制劑、錯合劑、氧化劑，以及至少一種磺酸鹽類陰離子表面活性劑组成；其中該腐蝕抑制劑為不含苯環的氮唑類化合物中的一種或多種。
- 如請求項1所述之化學機械研磨液，其中該磺酸鹽類陰離子表面活性劑為烷基磺酸鹽和/或烷基芳基磺酸鹽。
- 如請求項2所述之化學機械研磨液，其中該烷基磺酸鹽為C10~C18的烷基磺酸鹽，該烷基芳基磺酸鹽為C12~C18的烷基苯磺酸鹽，聚合度為200~600的聚苯乙烯磺酸鹽、4-乙烯基苯磺酸鹽和亞甲基萘磺酸鹽，其中，該鹽為鉀鹽和/或鈉鹽。
- 如請求項1所述之化學機械研磨液，其中該磺酸類陰離子表面活性劑含量為0.001~0.5wt%(重量百分比)。
- 如請求項4所述之化學機械研磨液，其中該磺酸類陰離子表面活性劑含量為0.005~0.1wt%。
- 如請求項1所述之化學機械研磨液，其中該研磨顆粒為二氧化矽溶膠。
- 如請求項1所述之化學機械研磨液，其中該研磨顆粒的粒徑為20~150奈米 (nanometer，nm)。
- 如請求項7所述之化學機械研磨液，其中該研磨顆粒的粒徑為50~120nm。
- 如請求項1所述之化學機械研磨液，其中該研磨顆粒的含量為0.05~2wt%。
- 如請求項9所述之化學機械研磨液，其中該研磨顆粒的濃度為0.1~1wt%。
- 如請求項1所述之化學機械研磨液，其中該錯合劑為氨羧化合物及其鹽。
- 如請求項11所述之化學機械研磨液，其中該錯合劑係選自甘氨酸、丙氨酸、纈氨酸、亮氨酸、脯氨酸、苯丙氨酸、酪氨酸、色氨酸、賴氨酸、精氨酸、組氨酸、絲氨酸、天冬氨酸、谷氨酸、天冬醯胺、穀氨醯胺、氨三乙酸、乙二胺四乙酸、環己二胺四乙酸、乙二胺二琥珀酸、二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一種或多種。
- 如請求項1所述之化學機械研磨液，其中該錯合劑含量為0.1~5wt%。
- 如請求項13所述之化學機械研磨液，其中該錯合劑含量為0.5~3wt%。
- 如請求項1所述之化學機械研磨液，其中該腐蝕抑制劑係選自1，2，4-三氮唑、3-氨基-1，2，4-三氮唑、4-氨基-1，2，4-三氮唑、3，5-二氨基-1，2， 4-三氮唑、5-羧基-3-氨基-1，2，4-三氮唑、3-氨基-5-巰基-1，2，4-三氮唑、5-乙酸-1H-四氮唑、5-甲基四氮唑和5-氨基-1H-四氮唑中的一種或多種。
- 如請求項1所述之化學機械研磨液，其中該腐蝕抑制劑的含量為0.001~2wt%。
- 如請求項16所述之化學機械研磨液，其中該腐蝕抑制劑的含量為0.005~1wt%。
- 如請求項1所述之化學機械研磨液，其中該氧化劑為過氧化氫。
- 如請求項1所述之化學機械研磨液，其中該氧化劑的濃度為0.05~5wt%。
- 如請求項19所述之化學機械研磨液，其中該氧化劑的濃度為0.1~3wt%。
- 如請求項1~20任一所述之化學機械研磨液，其中該化學機械研磨液的pH為5~8。
- 一種如請求項1~20所述的化學機械研磨液在金屬銅的研磨中的應用。
- 如請求項22所述的化學機械研磨液在金屬銅的研磨中的應用，其中該化學機械研磨液的pH為5~8。
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