TW201802874A - 於基底上形成定向自組裝層之方法 - Google Patents

於基底上形成定向自組裝層之方法 Download PDF

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TW201802874A
TW201802874A TW106112840A TW106112840A TW201802874A TW 201802874 A TW201802874 A TW 201802874A TW 106112840 A TW106112840 A TW 106112840A TW 106112840 A TW106112840 A TW 106112840A TW 201802874 A TW201802874 A TW 201802874A
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維爾納 內本
強 威廉 梅斯
馬丁 斯托克霍夫
羅爾 葛漢德
哈利 琶森吉 斯里拉曼
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Ａｓｍ Ｉｐ控股公司
愛美科公司
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Abstract

一種藉由以下步驟於基底上形成定向自組裝（DSA）層之方法：提供基底；在所述基底上施加包含自組裝材料的層；以及藉由在所述基底周圍提供受控的溫度及受控的氣體環境而將所述層的所述自組裝材料退火以形成定向自組裝層。所述受控的氣體環境以介於10帕至2000帕之間的分壓包含含有氧元素的分子。

Description

於基底上形成定向自組裝層之方法
本發明可有關於一種於基底上形成定向自組裝（directed self-assembled，DSA）層之方法。所述方法可例如包括：提供基底；在所述基底上施加包含自組裝材料的層；以及藉由在所述基底周圍提供受控的溫度及受控的氣體環境而將所述層的所述自組裝材料退火以形成定向自組裝層。
半導體裝置的大小已被推動以使其變得越來越小。不同的圖案化技術已被開發出來達成該些較小的大小。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）及間隔壁界定雙重圖案化（Spacer Defined Double patterning）。該些方式能夠在半導體裝置上產生亞25奈米（sub-25 nm）解析度圖案。
定向自組裝（DSA）已被視為一種用於未來微影應用的選項。定向自組裝可涉及使用嵌段共聚物（block copolymer）來界定用於自組裝的圖案。嵌段共聚物可包括聚(甲基丙烯酸甲酯)（poly(methyl methacrylate)，PMMA）或聚苯乙烯（polystyrene，PS），例如（舉例而言）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「高嵌段（high-Chi）」聚合物，其可潛在地達成小的尺寸。
嵌段共聚物可在一定條件下發生相分離以形成週期性奈米結構，如在聚(苯乙烯-嵌段-甲基丙烯酸甲酯)中一般。相分離是類似於油與水的分離的情況。油與水由於它們是相分離的而不混溶。由於嵌段之間的不相容性，嵌段共聚物可經歷相分離。由於不相容的嵌段彼此共價鍵合，因此它們無法在宏觀上分離。在「相分離」期間，嵌段會形成奈米大小的結構，其中不相容的嵌段最大限度地分離的同時仍然彼此共價鍵合，而相容嵌段則可藉由找到相似的相鄰嵌段而最大限度地組合在一起。端視每一嵌段的相對長度而定，可獲得若干個結構。
定向自組裝可用於例如以非常小的節距及臨界尺寸（critical dimension）形成平行線及空間結構或規則的孔陣列。具體而言，定向自組裝可在由表面形貌（surface topography）及/或表面化學圖案化引導的同時，藉由自組裝來界定亞25奈米辨析度圖案。
定向自組裝的缺點可能在於所獲得的平行線或孔陣列的結構可能在隨機位置具有某些缺陷。所述缺陷可由退火步驟中的不充分的相分離（例如自組裝）造成。
對於線陣列而言，當完全相分離的兩條平行線在同一位置被非相分離區域（橋）中斷時；或者進一步被線的平行配置在某一位置畸變的錯位（dislocation）中斷時，可例如藉由橋來界定所述缺陷。
本發明的目標在於例如提供一種改良的或至少替代性的於基底上形成定向自組裝（DSA）層之方法。
因此，在實施例中可提供一種於基底上形成定向自組裝（DSA）層之方法，所述方法包括：提供基底；在所述基底上施加包含自組裝材料的層；以及藉由在所述基底周圍提供受控的溫度及受控的氣體環境而將所述層的所述自組裝材料退火以形成定向自組裝層，其中所述方法包括將所述受控的氣體環境控制成以介於10帕至2000帕之間的分壓包含含有氧元素的分子。
藉由將所述層的所述自組裝材料退火以在所述基底周圍在受控的溫度下及受控的氣體環境中形成定向自組裝層，定向自組裝層中的缺陷的數目可減少，其中所述方法包括將所述受控的氣體環境控制成以介於10帕至2000帕之間的分壓、較佳地介於50帕至1000帕之間的分壓、且最佳地介於200帕至500帕之間的分壓來包含含有氧元素的分子。
根據再一實施例，提供一種被構造及被配置成在基底上形成定向自組裝（DSA）層的設備，所述設備包括：反應室，所述反應室被構造及被配置成容納所述基底；加熱元件，被配置成對所述基底上的層執行退火；以及氣體控制系統，控制所述反應室中所述基底周圍的所述氣體環境，其中所述方法包括將所述受控的氣體環境控制成以介於10帕至2000帕之間的分壓包含含有氧元素的分子。
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。
圖1說明根據本發明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自組裝材料的基底（例如晶圓）。所述晶圓可具有至少一種DSA定向自組裝材料，所述定向自組裝材料除其他聚合物外尤其包含聚甲基丙烯酸甲酯及聚苯乙烯（PS）。處理室可為批次式反應器或具有兩個批次式反應器的群集工具。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可包括執行定向自組裝聚合物的自組裝退火的第二步驟120。退火製程的目的是激發自組裝，例如定向自組裝聚合物（例如嵌段共聚物）中的自組織。換言之，聚合物中的平行線或孔的格網可根據基底上的引導結構的定向而形成。根據本發明的至少一個實施例，此可意味著聚甲基丙烯酸甲酯的域以及聚苯乙烯的域可以交替的方式形成。藉由自組裝退火達成的益處可包括改良自組裝製程、減少缺陷、改良線邊緣/寬度粗糙度以及改良臨界尺寸（CD）均勻性。另外，第二步驟120的退火可具有自聚合物排出濕氣或其它污染物、使聚合物硬化或者自基底表面選擇性地燒掉一種聚合物類型的目的。
為了在所獲得的圖案中達到低缺陷密度，製程參數（例如時間、溫度以及退火製程的環境條件及壓力）是至關重要的。可能需要長的退火時間才能獲得低的缺陷密度。退火可藉由在晶片周圍以介於100℃至400℃之間的溫度、較佳地介於200℃至300℃之間的溫度及最佳地約250℃的溫度提供受控的溫度環境來達成。退火可進行介於四分之一小時至四小時內、較佳地半小時至兩小時內且最佳地約1小時。端視相分離的速度而定，亦可為其他溫度及持續時間。然而，自組裝退火的溫度不應增加太高，否則聚合物可能會開始分解。
退火可在晶圓周圍的受控氣體環境中完成，晶圓周圍的受控氣體環境可包含氮氣、氬氣、氦氣、氫氣、氧氣、一氧化二氮、臭氧、水蒸氣、溶劑蒸氣或該些氣體的混合物。
藉由對自組裝材料進行退火來在基底周圍的受控溫度及氣體環境中形成定向自組裝層，定向自組裝層中的缺陷數目減少，其中將受控的氣體環境控制成以介於10帕至2000帕之間的分壓、較佳地介於50帕至1000帕之間的分壓且最佳地介於200帕至500帕之間的分壓包含含有氧元素的分子。退火被配置成在自組裝材料內引發定向自組裝。
含有氧元素的分子可選自包括氧氣（O2 ）、水（H2 O）及一氧化二氮（N2 O）的群組。
受控的氣體環境可包含至少一種惰性氣體，例如（舉例而言），氮氣（N2 ）、氬氣（Ar）或氦氣（He）。
退火與膜沈積可在位於同一群集工具上的不同反應室內進行或者可在不同的群集工具的不同的反應式室內執行。反應室可為用於處理基底的批次式系統。反應室可被配置成處理多個基底。
對層進行施加及對層進行退火可在單個反應室內進行。對層進行施加及對層進行退火可在位於同一工具中的不同的反應室內進行。反應室可為用於處理基底的批次式系統。反應室可被配置成處理多個基底。
退火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，批次式反應器可被證實有益於達成需要相當長退火時間的製程。批次式反應器可容納介於2個與250個之間的基板、較佳地容納介於5個與150個之間的基板或最佳地容納約100個基板。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。
圖2是示出在根據本發明的退火方法之後每平方公分的缺陷密度的曲線圖。圖2繪示出Y軸上的缺陷數目與X軸上的含有氧元素的分子（例如氧氣）的濃度的函數關係。線201繪示出在退火期間每平方公分的缺陷總數目與氧氣濃度的函數關係。線202繪示出在退火期間每平方公分的錯位總數目與氧氣濃度的函數關係。線203繪示出在退火期間每平方公分的橋總數目與氧氣濃度的函數關係。線204繪示出在退火期間每平方公分的殘渣總數目與氧氣濃度的函數關係。所述圖可表明在退火期間氧氣的與10帕至2000帕之間的分壓對應的0.01%至2%之間的濃度、較佳地與50帕至1000帕之間的分壓對應的0.05%至1%之間的濃度及最佳地與介於200帕至500帕之間的分壓對應的0.2%至0.5%之間的濃度可在此實驗中減少缺陷。
所示出及闡述的特定實施方案用以說明本發明及其最佳方式，而絕非旨在以其他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，可以所示順序及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
201、202、203、204‧‧‧線
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是根據本發明至少一個實施例的方法的流程圖。 圖2是示出在根據本發明的退火方法之後的每平方公分的缺陷密度的曲線圖。 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

Claims (21)

  1. 一種於基底上形成定向自組裝層之方法，包括： 提供基底； 在所述基底上施加包含自組裝材料的層；以及 藉由在所述基底周圍提供受控的溫度及受控的氣體環境而將所述層的所述自組裝材料退火以形成定向自組裝層，其中所述方法包括將所述受控的氣體環境控制成以介於10帕至2000帕之間的分壓包含含有氧元素的分子。
  2. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述方法包括將所述受控的氣體環境控制成以介於50帕至1000帕之間的分壓包含含有氧元素的分子。
  3. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述方法包括將所述受控的氣體環境控制成以介於200帕至500帕之間的分壓包含含有氧元素的分子。
  4. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述含有氧元素的分子選自包括氧氣、水及一氧化二氮的群組。
  5. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述方法包括將所述受控的氣體環境控制成包含至少一種惰性氣體。
  6. 如申請專利範圍第5項所述的於基底上形成定向自組裝層之方法，其中所述惰性氣體包括氮氣、氬氣或氦氣。
  7. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中在退火期間，所述受控的溫度被控制至100℃至400℃之間的範圍、較佳地200℃至300℃之間的範圍、或者更佳地控制至約250℃。
  8. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述自組裝材料包括二嵌段共聚物，其中所述嵌段中的至少一個包括聚苯乙烯或聚甲基丙烯酸甲酯。
  9. 如申請專利範圍第8項所述的於基底上形成定向自組裝層之方法，其中所述二嵌段共聚物包括聚(苯乙烯-嵌段-甲基丙烯酸甲酯)（PS-b-PMMA）。
  10. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述退火與所述膜沈積是在位於同一群集工具上的不同反應室內進行。
  11. 如申請專利範圍第10項所述的於基底上形成定向自組裝層之方法，其中所述反應室是用於處理基底的批次式系統。
  12. 如申請專利範圍第10項所述的於基底上形成定向自組裝層之方法，其中所述反應室被配置成處理多個基底。
  13. 如申請專利範圍第10項所述的於基底上形成定向自組裝層之方法，其中所述反應室被配置成處理多個基底。
  14. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述退火用以配置在所述自組裝材料內引發定向自組裝。
  15. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述退火步驟的溫度較所述膜沈積的溫度高至少25℃，較佳地較所述膜沈積的所述溫度高25℃至300℃，或者更佳地較所述膜沈積的所述溫度高100℃至250℃。
  16. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中施加所述層與將所述層退火是在單個反應室內進行。
  17. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中施加所述層與將所述層退火是在位於同一工具中的不同反應室內進行。
  18. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述方法包括在藉由在所述基底周圍提供受控的溫度及受控的氣體環境而在將所述自組裝材料退火之前對所述基底上的所述自組裝材料進行預退火，其中所述方法包括將所述受控的氣體環境控制成以10帕至2000帕的分壓包含含有氧元素的分子。
  19. 如申請專利範圍第1項所述的於基底上形成定向自組裝層之方法，其中所述受控的氣體環境具有100.000帕左右的壓力。
  20. 一種被構造及被配置以在基底上形成定向自組裝層的設備，所述設備包括： 反應室，所述反應室被構造及被配置成容納所述基底； 加熱元件，被配置成對所述基底上的層執行退火；以及 氣體控制系統，控制所述反應室中所述基底周圍的氣體環境，其中所述方法包括將受控的所述氣體環境控制成以介於10帕至2000帕之間的分壓包含含有氧元素的分子。
  21. 如申請專利範圍第18項所述的方法，其中所述加熱元件被構造及被配置成在退火期間將所述受控的溫度控制至100℃至400℃的範圍、較佳地200℃至300℃的範圍、或者更佳地控制至約250℃。
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