TWI707971B - 複合退火以及選擇性沈積製程 - Google Patents

複合退火以及選擇性沈積製程 Download PDF

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TWI707971B
TWI707971B TW106112725A TW106112725A TWI707971B TW I707971 B TWI707971 B TW I707971B TW 106112725 A TW106112725 A TW 106112725A TW 106112725 A TW106112725 A TW 106112725A TW I707971 B TWI707971 B TW I707971B
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film
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強 威廉 梅斯
維爾納 內本
羅爾 葛漢德
艾爾君 辛區
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荷蘭商Ａｓｍ Ｉｐ控股公司
比利時商愛美科公司
魯汶天主教大學
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Abstract

揭露一種使用退火步驟及沈積步驟來形成膜的方法。所述方法包括用於在聚合物內誘發自組裝或對齊的退火步驟。所述方法亦包括選擇性沈積步驟以在聚合物上達成選擇性沈積。

Description

複合退火以及選擇性沈積製程 [相關申請案的交叉參考]
本申請案與2016年4月18日提出申請且標題為「複合退火以及選擇性沈積系統(COMBINED ANNEAL AND SELECTIVE DEPOSITION SYSTEMS)」的美國非臨時專利申請案15/132,084、及2016年4月18日提出申請且標題為「於基底上形成定向自組裝層之方法(METHOD OF FORMING A DIRECTED SELF-ASSEMBLED LAYER ON A SUBSTRATE)」的美國臨時專利申請案62/324,255相關，所述美國非臨時專利申請案及所述美國臨時專利申請案的揭露內容全文併入本案供參考。
本發明大體而言是有關於用於製造電子裝置的製程及系統。更具體而言，本發明是有關於膜的選擇性沈積。詳細而言，本發明可揭露選擇性地形成膜的方法及系統，所述選擇性地形成膜的方法及系統使用定向自組裝(directed self-assembly，DSA)圖案化技術。
隨著發展趨勢已推動半導體元件的大小變得越來越小，且已出現了不同的圖案化技術。該些技術包括間隔壁界定四重圖案化(spacer defined quadruple patterning)、極紫外光微影(extreme ultraviolet lithography，EUV)、及結合間隔壁界定雙重圖案化(Spacer Defined Double patterning)的極紫外光微影。該些方式已使得能夠生產出介於7奈米(nm)範圍內的節點。
定向自組裝(directed self-assembly，DSA)已被視為一種針對未來微影應用的選擇方案。定向自組裝涉及使用嵌段共聚物(block copolymer)界定圖案以達成自組裝。所使用的嵌段共聚物可包括聚(甲基丙烯酸甲酯)(poly(methyl methacrylate)，PMMA)、聚苯乙烯(polystyrene，PS)、或聚(苯乙烯-嵌段-甲基丙烯酸甲酯)(poly(styrene-block-methyl methacrylate)，PS-b-PMMA)。其他嵌段共聚物可包括新興的「高相互作用參數(high interaction parameter；high-Chi)」聚合物，其可潛在地達成小的尺寸。
定向自組裝可用於形成具有非常小的節距及臨界尺寸(critical dimension，CD)的平行線或規律的孔/柱/桿陣列。具體而言，定向自組裝可在利用表面地形學(surface topography)及/或表面化學圖案化(surface chemical patterning)進行引導的同時藉由自組裝來界定亞20奈米圖案。因此，可以前驅物對定向自組裝聚合物層進行滲透，或者可在定向自組裝聚合物層的聚合物中的一者上選擇性地沈積膜。
然而，定向自組裝技術具有若干缺點。具體而言，定向 自組裝聚合物(例如，PMMA或聚苯乙烯)具有低耐蝕刻性(etch resistance)。此使得更難以將圖案轉送至位於下方的層。由於使半導體裝置的大小進一步按比例縮小所需的高級聚合物具有更低的耐蝕刻性及蝕刻選擇性，因此低耐蝕刻性這一問題變得愈發嚴峻。另外，定向自組裝可能在所得圖案中造成高的線邊緣粗糙度(line edge roughness)。另一缺點是平行線或孔陣列的所得結構可能在任意位置處具有某些缺陷。
因此，需要一種用於選擇性地形成具有較高耐蝕刻性及蝕刻選擇性的膜的方法。
根據本發明的至少一個實施例，揭露一種選擇性地形成膜的方法。所述方法包括：在反應室中提供供處理的基底，所述基底具有設置於所述基底上的至少一個聚合物層；對所述基底執行退火步驟；以及藉由將第一前驅物及第二前驅物依序脈衝至所述基底上來執行膜沈積，所述膜沈積用以達成至少所述第一前驅物向所述至少一個聚合物層中的滲透，其中自所述反應室吹洗所述第一前驅物的及所述第二前驅物的過量部分；其中於所述至少一個聚合物層上，由所述第一前驅物形成第一膜。
根據本發明的至少一個實施例，揭露一種用於選擇性地形成膜的方法。所述方法可包括：在反應室中提供供處理的基底，所述基底具有設置於所述基底上的至少一個聚合物層；藉由將第一前驅物及第二前驅物依序脈衝至所述基底上來執行膜沈積，所 述膜沈積用以達成至少所述第一前驅物向所述至少一個聚合物層中的滲透，其中自所述反應室吹洗所述第一前驅物的及所述第二前驅物的過量部分；以及對所述基底執行退火步驟；其中於所述至少一個聚合物層上，由所述第一前驅物形成膜。
為了總結本發明及藉由先前技術而達成的優點，以上在本文中闡述了本發明的某些目標及優點。當然，應理解，未必根據本發明的任一特定實施例均可達成所有這些目標及優點。因此，舉例而言，熟習此項技術者將認識到本發明可以如下方式實施或施行：所述方式會使得達成或優化本文中所教示或提出的一個優點或一組優點，但未必會達成本文中所可能教示或提出的其他目標或優點。
所有該些實施例皆旨在落於本文所揭露本發明的範圍內。藉由參照附圖閱讀對某些實施例的以下詳細說明，對於熟習此項技術者而言該些及其他實施例將變得顯而易見，本發明不僅限於所揭露的任意一或多個特定實施例。
儘管以下揭露某些實施例及實例，然而，熟習此項技術者應理解，本發明會擴展超出所具體揭露的實施例及/或本發明的用途以及其明顯潤飾及等效形式。因此，旨在使所揭露本發明的範圍不應受限於以下所述特定所揭露實施例。
根據本發明的實施例是有關於定向自組裝技術與選擇性沈積的組合。此種組合可顯著提高聚合物的耐蝕刻性。選擇性沈積使特定聚合物能夠與前驅物氣體進行反應，而使其他聚合物不被接觸。
將選擇性沈積與定向自組裝圖案化加以組合可提供在先前方式（例如，在美國專利公開案第US 2014/0273514 Al號中闡述的方式）中前所未見的益處。舉例而言，在90℃下選擇性地沈積氧化鋁（Al2 O3 ）可使得能夠與PMMA聚合物進行反應，而使聚苯乙烯聚合物不被接觸。氧化鋁將不僅沈積於PMMA聚合物的頂上，而且可被灌注至PMMA聚合物中以提高PMMA聚合物的剛性（rigidity）。
圖1說明根據本發明的至少一個實施例的方法100。方法100包括第一步驟110，第一步驟110在處理室中提供具有多個聚合物的晶圓。如上所述，所述晶圓可具有至少第一定向自組裝聚合物及第二定向自組裝聚合物，其中第一定向自組裝聚合物及第二定向自組裝聚合物可由PMMA、聚苯乙烯（PS）、及其他聚合物製成。處理室可為批量反應器（batch reactor）或具有兩個批量反應器的集群工具（cluster tool）。潛在處理室的一個實例可包括來自ASM國際公眾有限公司（ASM International N.V.）的A412系統，其可在兩個反應室中運行相同的製程或者獨立地或依序地運行兩個不同的製程。
方法100可包括第二步驟120，第二步驟120對定向自組裝聚合物執行自組裝退火（self-assembly anneal）。退火製程的目的是在定向自組裝聚合物或嵌段共聚物中引起自組裝或自組織（self-organization）。換言之，可隨著藉由基底上的引導結構進行定向來形成聚合物中的平行線或孔/柱/桿的柵格（grid）。根據本發明的至少一個實施例，此可意指可以交替的方式形成PMMA域（domain）及PS域。藉由自組裝退火而達成的益處可包括自組裝製程的改善、缺陷的減少、線寬粗糙度的提高、及臨界尺寸（CD）均勻性的提高。作為另一選擇，第二步驟120的退火可用於自聚合物脫去水分或其他污染物、使聚合物硬化、或自基底表面選擇性地燒掉各聚合物類型中的一種。
為了在所得圖案中達成低缺陷密度（defect density），例如退火製程的時間、溫度、及周圍條件及壓力等的製程參數是至關重要的。獲得低缺陷密度可需要長的退火時間。退火可在範圍介於100℃與400℃之間、較佳地介於200℃與300℃之間、且最佳地為250℃的溫度下進行約60分鐘。根據所需的退火量，可存在其他溫度及持續時間。然而，自組裝退火的溫度不應升高到過高，不然聚合物可能會開始分解。
在其中進行退火的周圍環境可包括氮氣、氬氣、氦氣、氫氣、氧氣、臭氧、水蒸氣、溶劑蒸氣（solvent vapor）、或該些氣體的混合物。退火周圍環境的壓力可為介於極高真空（ultra-high vacuum）至大氣壓範圍內的任意壓力或甚至高於大氣壓。
根據本發明的一個實施例，可在單一晶圓熱板（wafer hot plate）上進行退火製程。根據本發明的另一實施例，批量反應器可證實為有益於達成需要長退火時間的製程。批量反應器可容納介於2個與250個之間的基底、較佳地容納介於5個與150個之間的基底、或最佳地容納約100個基底。舉例而言，可以使得可對退火製程使用一個反應器的方式來操作A412。此可使得能夠以成本有效的方式執行大約1至2小時的長時間退火。
方法100亦可包括第三步驟130，第三步驟130執行在第一定向自組裝聚合物或第二定向自組裝聚合物頂上選擇性地沈積金屬或者介電質膜或材料的選擇性沈積。如此一來，可以使得所沈積膜可選擇性地與兩個聚合物中的僅一者進行反應的方式進行選擇性沈積。舉例而言，可以使得所沈積膜可與PMMA聚合物而非PS聚合物進行反應的方式進行選擇性沈積。根據本發明的至少一個實施例，第三步驟130可包括金屬或介電質膜的原子層沈積（atomic layer deposition）。
此外，可以進行所述選擇性沈積，以使得所經沈積的金屬或介電質膜可滲透聚合物、同時亦在聚合物域的整個體積上沈積第二膜。根據本發明的至少一個實施例，第三步驟130可在A412系統的一個反應器中進行，使得第二步驟120在A412系統的另一反應器中進行。第二步驟120與第三步驟130亦可在A412系統的一個單一反應器中進行。
在第三步驟130中沈積的金屬或介電質可包括氧化鋁（Al2 O3 ）、二氧化矽（SiO2 ）、氮化矽（SiN）、碳氧化矽（SiOC）、碳氮化矽（SiCN）、氮化鋁（AlN）、氮化鈦（TiN）、氮化鉭（TaN）、鎢（W）、鈷（Co）、二氧化鈦（TiO2 ）、氧化鉭（Ta2 O5 ）、二氧化鋯（ZrO2 ）、或二氧化鉿（HfO2 ）。為了執行選擇性沈積，可使用用以獲得所述金屬的前驅物（例如三甲基鋁（trimethylaluminum，TMA）及水（H2 O））來形成Al2 O3 。
第三步驟130中的選擇性沈積可在範圍介於25℃與300℃之間的溫度（其中較佳溫度範圍為70℃至90℃）下進行，以形成Al2 O3 。在第三步驟130期間的溫度可小於在第二步驟120期間的溫度，因此可需要冷卻步驟以將為250℃的示例性退火溫度降低至為70℃的第三步驟130溫度。根據本發明的至少一個實施例，第二步驟120的溫度較第三步驟130的溫度高至少25℃，較佳地較第三步驟130的溫度高25℃至300℃之間、或更佳地較第三步驟130的溫度高100℃至250℃之間。
第三步驟130可包括對第一前驅物（例如，TMA）進行持續時間介於30秒至10分鐘範圍內的第一脈衝。第三步驟130亦可接著包括進行持續時間介於10至60秒範圍內的吹洗。第三步驟130可接著包括對第二前驅物（例如，水）進行持續時間介於10至60秒範圍內的脈衝。第三步驟130可接著包括持續時間介於10秒至2分鐘範圍內的第二吹洗。另外，可視需要重複進行第三步驟130，以達成對金屬的充分沈積。
根據本發明的至少一個實施例，為膜沈積的第三步驟130可在為退火的第二步驟120之前進行。在此種情形中，金屬或介電質膜可首先滲透聚合物，且接著可進行退火製程。作為退火製程的結果，可在第二步驟120中燒掉在第三步驟130期間未與金屬或介電質膜反應的聚合物。
方法100亦可包括第四步驟140，第四步驟140對前驅物進行吹洗。第四步驟140可涉及引入吹洗氣體，例如氮氣、氦氣、氬氣、及其他惰性氣體。吹洗氣體將自處理室移除來自第四步驟140的過量前驅物。第四步驟140可在與第三步驟130的溫度相似的溫度下進行。
根據本發明的至少一個實施例，可在必要時重複進行第三步驟130以使得前驅物能夠向定向自組裝聚合物中滲透。可將所述循環重複近似5次，以確保定向自組裝聚合物中具有足量的金屬或介電質膜。在每一循環中，第三步驟130的持續時間可為大約幾分鐘。利用該些持續時間，批量反應器可用於藉由一次處理多達100個或以上的晶圓來達成高生產率及低處理成本。
根據本發明的至少一個實施例，可以使得可以脈衝-吹洗-脈衝-吹洗的方式重複進行第三步驟130的方式來操作方法100。可將該些步驟的條件設定為較高壓力及較長時間，以使得前驅物能夠滲透聚合物。以此種方式進行的單一循環的持續時間的範圍介於1分鐘與20分鐘之間。可將所述循環重複進行若干次（通常為五次），以達成材料在聚合物內的充分沈積。由於聚合物內的材料的滲透可能耗費較長的時間量，因此複合退火及沈積製程提供了以批量方式執行各步驟的機會。
複合退火及選擇性沈積製程的使用的潛在應用可為用於極紫外光（extreme ultraviolet，EUV）光阻。用於極紫外光應用的退火可能無法用於聚合物的自組裝，但可用於進行固化或穩定。舉例而言，根據本發明至少一個實施例的複合退火及選擇性沈積製程可幫助達成依續滲透合成（sequential infiltration synthesis，SIS）步驟，乃因所述製程能潛在地防止羧基轉化、或者能自聚合物膜脫去水分或對光阻進行穩定化或硬化。
示出及闡述特定實施方案是用以說明本發明及其最佳方式，而絕非旨在以另一方式限制各態樣及實施方案的範圍。事實上，為簡明起見，可能未詳細闡述所述系統的傳統製造、連接、準備、及其他功能性態樣。此外，各種圖中所示的連接線旨在代表各種元件之間的示例性功能性關係及/或實體耦合。在實際系統中可存在諸多替代性或附加功能性關係或者實體連接，及/或在某些實施例中可不存在所述替代性或附加功能性關係或者實體連接。
應理解，本文所述配置及/或方式本質上是示例性的，且該些具體實施例或實例不應被視為具有限制意義，乃因可存在眾多變型。本文所述具體例程或方法可代表任意數目的處理策略中的一或多者。因此，可以所示順序、以其他順序執行所示各種動作，或在某些情形中省略各所示動作。
本發明的主題包括本文所揭露的各種製程、系統、及配置與其他特徵、功能、動作、及/或性質的所有新穎及非顯而易見的組合及子組合、以及其任意及所有等效形式。
100‧‧‧方法 110‧‧‧第一步驟 120‧‧‧第二步驟 130‧‧‧第三步驟 140‧‧‧第四步驟
以下參照某些實施例的圖式來闡述本文所揭露本發明的該些及其他特徵、態樣、及優點，所述圖式旨在說明而非限制本發明。
圖1是根據本發明的至少一個實施例的方法的流程圖。
應理解，圖中的元件是出於簡潔及清晰的目的而示出且未必是按比例繪製。舉例而言，圖中的某些元件的尺寸可相對於其他元件而言被誇大以幫助增強對本發明的所示實施例的理解。
100‧‧‧方法
110‧‧‧第一步驟
120‧‧‧第二步驟
130‧‧‧第三步驟
140‧‧‧第四步驟

Claims (24)

  1. 一種選擇性地形成膜的方法，包括：在反應室中提供供處理的基底，所述基底具有設置於所述基底上的至少一個聚合物層；對所述基底執行退火步驟；以及在低於所述退火步驟溫度的溫度下藉由將第一前驅物及第二前驅物依序脈衝至所述基底上來執行膜沈積，所述膜沈積用以達成至少所述第一前驅物向所述至少一個聚合物層中的滲透，其中自所述反應室吹洗所述第一前驅物的及所述第二前驅物的過量部分；其中，於所述至少一個聚合物層上，由所述第一前驅物形成第一膜，以及其中所述膜沈積包括：將所述第一前驅物脈衝至所述基底上；自所述反應室吹洗所述第一前驅物；將所述第二前驅物脈衝至所述基底上；以及自所述反應室吹洗所述第二前驅物。
  2. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中於所述至少一個聚合物層內，由滲透所述至少一個聚合物層的所述第一前驅物形成第二膜。
  3. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述第一膜包含以下中的至少一者：氧化鋁(Al2O3)、二氧 化矽(SiO2)、氮化矽(SiN)、氮氧化矽(SiON)、碳氮化矽(SiCN)、氮化鋁(AlN)、氮化鈦(TiN)、氮化鉭(TaN)、鎢(W)、鈷(Co)、二氧化鈦(TiO2)、氧化鉭(Ta2O5)、二氧化鋯(ZrO2)、或二氧化鉿(HfO2)。
  4. 如申請專利範圍第2項所述的選擇性地形成膜的方法，其中所述第二膜包含以下中的至少一者：氧化鋁(Al2O3)、二氧化矽(SiO2)、氮化矽(SiN)、氮氧化矽(SiON)、碳氮化矽(SiCN)、氮化鋁(AlN)、氮化鈦(TiN)、氮化鉭(TaN)、鎢(W)、鈷(Co)、二氧化鈦(TiO2)、氧化鉭(Ta2O5)、二氧化鋯(ZrO2)、或二氧化鉿(HfO2)。
  5. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中在所述退火步驟的期間，所述反應室的溫度的範圍介於100℃與400℃之間。
  6. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中在所述膜沈積的期間，所述反應室的溫度的範圍介於25℃與300℃之間。
  7. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述至少一個聚合物層包含以下中的至少一者：聚(甲基丙烯酸甲酯)(PMMA)、聚苯乙烯、聚(苯乙烯-嵌段-甲基丙烯酸甲酯)(PS-b-PMMA)、或極紫外光光阻。
  8. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述基底包含第二聚合物。
  9. 如申請專利範圍第8項所述的選擇性地形成膜的方法，其中所述第二聚合物包括以下中的至少一者：聚(甲基丙烯酸甲酯)(PMMA)、聚苯乙烯、聚(苯乙烯-嵌段-甲基丙烯酸甲酯)(PS-b-PMMA)、或極紫外光光阻。
  10. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中吹洗所述第一前驅物的所述過量部分包括使用以下中的至少一者來吹洗所述反應室：氮氣(N2)、氬氣(Ar)、或氦氣(He)。
  11. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中執行所述膜沈積的步驟是重複地進行以每次重複形成更大厚度的所述第一膜。
  12. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述退火步驟與所述膜沈積是在單一反應室內進行。
  13. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述反應室是用於處理基底的批量系統。
  14. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述反應室用以處理多個基底。
  15. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述退火步驟用以在所述至少一個聚合物層內誘發自組裝。
  16. 如申請專利範圍第1項所述的選擇性地形成膜的方法，其中所述退火步驟的溫度較所述膜沈積的溫度高至少25℃。
  17. 一種選擇性地形成膜的方法，包括： 在反應室中提供供處理的基底，所述基底具有設置於所述基底上的至少一個聚合物層；對所述基底執行退火步驟；以及藉由將第一前驅物及第二前驅物依序脈衝至所述基底上來執行膜沈積，所述膜沈積用以達成至少所述第一前驅物向所述至少一個聚合物層中的滲透，其中自所述反應室吹洗所述第一前驅物的及所述第二前驅物的過量部分；其中，於所述至少一個聚合物層上，由所述第一前驅物形成第一膜，以及其中所述退火步驟與所述膜沈積是在位於同一集群工具上的不同反應室內進行。
  18. 一種選擇性地形成膜的方法，包括：在反應室中提供供處理的基底，所述基底具有設置於所述基底上的至少一個聚合物層；藉由將第一前驅物及第二前驅物依序脈衝至所述基底上來執行膜沈積，所述膜沈積用以達成至少所述第一前驅物向所述至少一個聚合物層中的滲透，其中自所述反應室吹洗所述第一前驅物的及所述第二前驅物的過量部分；以及在執行所述膜沈積後，在高於所述膜沈積溫度的溫度下對所述基底執行退火步驟；其中於所述至少一個聚合物層上，由所述第一前驅物形成所述膜，以及其中所述膜沈積包括：將所述第一前驅物脈衝至所述基底上； 自所述反應室吹洗所述第一前驅物；將所述第二前驅物脈衝至所述基底上；以及自所述反應室吹洗所述第二前驅物。
  19. 如申請專利範圍第18項所述的選擇性地形成膜的方法，其中所述退火步驟與所述膜沈積是在單一反應室內進行。
  20. 如申請專利範圍第18項所述的選擇性地形成膜的方法，其中所述反應室是用於處理基底的批量系統。
  21. 如申請專利範圍第18項所述的選擇性地形成膜的方法，其中所述反應室用以處理多個基底。
  22. 如申請專利範圍第18項所述的選擇性地形成膜的方法，其中所述退火步驟用以在所述至少一個聚合物層內誘發自組裝。
  23. 如申請專利範圍第18項所述的選擇性地形成膜的方法，其中所述退火步驟的溫度較所述膜沈積的溫度高至少25℃。
  24. 一種選擇性地形成膜的方法，包括：在反應室中提供供處理的基底，所述基底具有設置於所述基底上的至少一個聚合物層；藉由將第一前驅物及第二前驅物依序脈衝至所述基底上來執行膜沈積，所述膜沈積用以達成至少所述第一前驅物向所述至少一個聚合物層中的滲透，其中自所述反應室吹洗所述第一前驅物的及所述第二前驅物的過量部分；以及在執行所述膜沈積後，對所述基底執行退火步驟；其中於所 述至少一個聚合物層上，由所述第一前驅物形成所述膜，其中所述退火步驟與所述膜沈積是在位於同一集群工具上的不同反應室內進行。
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