TWI770310B - 用於間隔件界定圖案化之垂直間隔件的形成方法 - Google Patents

用於間隔件界定圖案化之垂直間隔件的形成方法 Download PDF

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TWI770310B
TWI770310B TW107140247A TW107140247A TWI770310B TW I770310 B TWI770310 B TW I770310B TW 107140247 A TW107140247 A TW 107140247A TW 107140247 A TW107140247 A TW 107140247A TW I770310 B TWI770310 B TW I770310B
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TW201935560A (zh
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久保田智廣
諏佐喜朗
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荷蘭商Ａｓｍ智慧財產控股公司
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Abstract

本發明係關於一種形成用於間隔件界定多重圖案化之垂直間隔件的方法，其包括：沉積具有第一膜應力之第一仿形圖案轉移膜，及將具有第二膜應力之第二仿形圖案轉移膜連續地沉積於模板上；乾式蝕刻除了核心材料及該等第一及第二圖案轉移膜之垂直部分外的該模板從而形成垂直間隔件；及乾式蝕刻該核心材料，從而在垂直間隔件之間形成閒置空間，其中經由調整該等第一及第二圖案轉移膜之間的膜應力差異來調整該等間隔件的傾斜角。

Description

用於間隔件界定圖案化之垂直間隔件的形成方法
本發明大致係關於一種在半導體製造過程中形成用於間隔件界定圖案化之垂直間隔件的方法。
使用微影技術之圖案化製程係半導體製造過程的基礎。然而，由於微影術中所使用之雷射光的有限波長，因而微影技術在圖案小型化中面臨困難。使用已知之圖案化技術實現圖案小型化的一種方法係SADP(自對準雙重圖案化)或SDDP(間隔件界定雙重圖案化)。圖4係根據一比較實施例之雙重圖案化的示意性圖示(步驟(a)至(c))。在步驟(a)中，將心軸(光阻劑)101圖案化作為下伏層102上之核心材料。在步驟(b)中，沉積膜103以覆蓋心軸101之經暴露表面及下伏表面102之經暴露表面的全體。在步驟(c)中，藉由乾式蝕刻，蝕刻膜103及心軸101之水平部分以形成間隔件104。藉由使用以上製程，由步驟(c)中之間隔件104所構成之圖案可具有步驟(a)中之光阻劑101之圖案之一半的間距，即可實現雙倍密度間距圖案化。然而，在該製程中，間隔件104(由膜103之側壁部分形成)在如圖4所示之核心剝除步驟(c)期間及之後朝閒置空間110傾斜。此傾斜現象使得半導體製造商很難精確地連續進行後續的積體製程。預期以上的傾斜問題將隨技術進步及小型化進展而變得更為嚴重。
在圖4中說明的以上習知圖案化中存在另一問題。亦即，由於間隔件104係由沉積於心軸101上之膜103形成，且沉積於各心軸101之頂部轉角的 膜103必然如步驟(b)中所示彎曲，因此由膜103之頂部轉角部分形成之間隔件104的頂部部分111在於步驟(c)中進行蝕刻時自然地變圓。此外，在步驟(c)之回蝕製程中，由於間隔件的頂部部分被來自電漿的離子轟擊侵襲(其中間隔件的外部部分較間隔件的內部部分更易受到離子轟擊)，因而間隔件104的圓形輪廓變得更為清楚及顯著，從而導致「肩部損失」。若肩部損失顯著，則需修整間隔件的頂部部分，藉此減小間隔件的高度。此肩部損失現象使得半導體製造商很難精確地連續進行後續的積體製程。預期以上的肩部損失問題將隨技術進步及小型化進展而變得更為嚴重。
關於相關技術之問題及解決方案的任何論述，僅為提供本發明之背景脈絡而包括於本揭示中，不應被視為同意該論述的任何或全部在本發明完成之際為已知。
為解決習知圖案化中之至少一個問題，在本發明之一些具體例中，間隔件係藉由使用雙層膜來形成，藉此控制經蝕刻間隔件的傾斜角，尤其係抑制或阻止間隔件向內傾斜，該角度係定義為各側壁部分之內面參考垂直於藉由移除間隔件間之核心材料所形成之閒置空間底部之線所測得之角度，其中傾斜角為零代表完全垂直及傾斜角為正值代表向內傾斜。雙層膜滿足兩層具有不同膜應力且兩者係高度仿形(較佳藉由原子層沉積(ALD)形成)的條件。藉由改變兩層間之膜應力的差異，可將間隔件的傾斜角控制至期望度數及期望方向(向內或向外)。換言之，藉由將外層調整為具有較內層高的壓縮應力(即外層在負方向中具有較內層大的應力值)，間隔件的傾斜角變得在正方向中較大，即向內傾斜。另一方面，藉由將內層調整為具有較外層高的壓縮應力(即內層在負方向中具有較外層大的應力值)，間隔件的傾斜角變得在負方向中較大，即向外傾斜。如此，藉由適切地調整構成間隔件之內層與外層間的膜應力差異，可將間隔件 的傾斜角調整至目標值。
此外，在一些具體例中，雙層膜滿足兩層具有不同程度之抗乾式蝕刻性的條件。藉由改變兩層間之乾式蝕刻速率的差異，可操控間隔件的頂部輪廓。特定言之，藉由將內層調整為具有較外層低之抗乾式蝕刻性(較高的乾式蝕刻速率)，可有效地防止肩部損失，且當形成間隔件時，間隔件的頂部可變得實質上平坦。因此，可省略進一步蝕刻來使得間隔件的頂部變平坦，即可維持間隔件的有效高度，該高度可視目標結構、圖案化方法等而改變。因此，當使用間隔件作為遮罩時，可加工厚的下伏層。此外，藉由將另一圖案轉移膜沉積於間隔件上，隨後進行各向異性蝕刻，可有效地進行自對準四重圖案化(SAQP)或間隔件界定四重圖案化(SDQP)(間隔件於間隔件上)。藉此，可加寬間隔件的應用。在SAQP或SDQP中，進行兩次分割間隔件之間距，藉此將解析度提高至11nm HP(半間距)。
為了概述本發明之態樣及相對於相關技術所達成之優點的目的，在本揭示中描述本發明之某些目標及優點。當然，應明瞭無須所有該等目的或優點皆可根據本發明之任何特定具體例來達成。因此，舉例而言，熟習此項技術者將認知到，可以如本文中所教示般地達成或最佳化一個優點或一組優點而無須達成本文中可能教示或建議之其他目標或優點的方式來體現或實施本發明。
本發明之其他態樣、特徵及優點將由隨後之詳細描述更加明白。
1‧‧‧基板
2‧‧‧電極
3‧‧‧反應室
4‧‧‧電極
5‧‧‧轉移室
6‧‧‧排氣管線
7‧‧‧排氣管線
11‧‧‧反應區
12‧‧‧電接地
13‧‧‧圓管
14‧‧‧分隔板
16‧‧‧轉移區
20‧‧‧HRF功率
21‧‧‧氣體管線
22‧‧‧氣體管線
23‧‧‧氣體管線
24‧‧‧氣體管線
60‧‧‧肩部部分
70‧‧‧矽基板
74‧‧‧第二垂直間隔件
81‧‧‧目標層
82‧‧‧蝕刻硬遮罩/第二模板
84‧‧‧垂直間隔件
93‧‧‧光阻劑圖案
94‧‧‧抗反射層
95‧‧‧雙層膜
96‧‧‧核心部分
101‧‧‧心軸(光阻劑)
102‧‧‧下伏層
102a‧‧‧底面
103‧‧‧膜
104‧‧‧間隔件
104a‧‧‧內面
105‧‧‧圖案轉移膜
105a‧‧‧第一層
105b‧‧‧第二層
106‧‧‧間隔件
106a‧‧‧內層
106b‧‧‧外層
107‧‧‧圖案轉移膜
107a‧‧‧第一層
107a1‧‧‧經蝕刻表面/經暴露表面
107a2‧‧‧經暴露表面
107a3‧‧‧經暴露表面
107a4‧‧‧經暴露表面
107b‧‧‧第二層
107b1‧‧‧經蝕刻表面/經暴露表面
107b2‧‧‧經暴露表面
107b3‧‧‧經暴露表面
107b4‧‧‧經暴露表面
107b5‧‧‧部分
107b6‧‧‧經暴露表面
108‧‧‧間隔件
108a‧‧‧內層
108b‧‧‧外層
110‧‧‧閒置空間
111‧‧‧間隔件
112‧‧‧頂部輪廓
現在將參看意欲說明而非限制本發明之較佳具體例的圖式來描述本發明之此等及其他特徵。該等圖式經大大簡化以用於說明性目的且未必按比例繪製。
圖1為可用於本發明之一具體例中的用於沉積保護膜之 PEALD(電漿增強型原子層沉積)設備之示意性圖式。
圖2係說明根據本發明之一具體例製造垂直間隔件結構之步驟的流程圖。
圖3係說明根據本發明之另一具體例調整垂直間隔件結構形狀之步驟的流程圖。
圖4係根據一比較實施例之雙重圖案化(步驟(a)至(c))之示意性圖式。
圖5係根據本發明之一具體例之雙重圖案化(步驟(a)至(c))的示意性圖式。
圖6係根據本發明之另一具體例之雙重圖案化(步驟(a)至(c))的示意性圖式。
圖7係根據本發明之一具體例製造於基板上之間隔件之橫截面圖的STEM(掃描式穿透電子顯微鏡)照片，該照片係用來顯示傾斜角。
圖8顯示橫截面圖的STEM照片，其中(a)及(b)顯示沉積於抗蝕劑圖案上之具有不同膜應力的氧化矽膜，及(c)及(d)分別顯示自(a)及(b)中顯示之膜形成的間隔件。
圖9顯示根據本發明之具體例之橫截面圖的STEM照片，其中(a)及(b)分別顯示圖8之(c)及(d)中顯示的間隔件，及(c)顯示由用於(a)中顯示之間隔件之內部氧化矽層及用於(b)中顯示之間隔件之外部氧化矽層組成的經沉積氧化矽膜，(d)顯示自(c)中顯示之膜形成的間隔件，(e)顯示由用於(b)中顯示之間隔件之內部氧化矽層及用於(b)中顯示之間隔件之外部氧化矽層組成的經沉積氧化矽膜，及(f)顯示自(e)中顯示之膜形成的間隔件。
圖10係顯示根據本發明之具體例，在傾斜角與雙層圖案轉移膜之外層與內層間之膜應力差異之間的關係圖。
圖11顯示用來顯示「肩部損失」之橫截面圖的STEM照片，其中(a)顯示自根據比較實施例之單層膜形成的間隔件，及(b)顯示自根據本發明之一具體例之雙層膜形成的間隔件。
圖12說明形成具有平坦頂部之間隔件的機制，其中(a)示意性地說明用來形成間隔件的雙層膜，及(b)至(f)係顯示根據本發明之一具體例之步驟的放大示意性部分圖。
圖13顯示橫截面圖的STEM照片，其顯示根據本發明之一具體例在步驟(a)至(f)中自雙層膜形成具有平坦頂部之間隔件的步驟。
圖14係根據本發明之一具體例使用間隔件界定雙重圖案化(SDDP)之圖案轉移及目標蝕刻(步驟(a)至(j))的示意性圖式。
圖15係說明根據本發明之另一具體例調整垂直間隔件結構之頂部輪廓之步驟的流程圖。
圖16說明根據本發明之一具體例在沉積具有不同膜應力之氧化矽膜之一個循環中的製程順序。
圖17說明根據本發明之一具體例在沉積具有不同膜應力之氮化矽膜之一個循環中的製程順序。
圖18係當間隔件係由多個層構成時(層數係n)，用來解說垂直間隔件之力學之垂直間隔件的示意性圖式。
圖19係當間隔件係由兩個層構成時，用來解說垂直間隔件之力學之垂直間隔件的示意性圖式。
在本揭示中，「氣體」可包括汽化之固體及/或液體且可由單一氣體或氣體混合物構成。在本揭示中，經由噴淋頭引入至反應室之製程氣體可包含前驅體氣體及添加劑氣體、基本上由前驅體氣體及添加劑氣體組成或由前 驅體氣體及添加劑氣體組成。前驅體氣體及添加劑氣體通常係作為混合氣體或個別地引入至反應空間。前驅體氣體可利用載氣(諸如稀有氣體)引入。添加劑氣體可包含反應物氣體及稀釋氣體(諸如稀有氣體)、基本上由反應物氣體及稀釋氣體(諸如稀有氣體)組成或由反應物氣體及稀釋氣體(諸如稀有氣體)組成。反應物氣體及稀釋氣體可作為混合氣體或個別地引入至反應空間。前驅體可包含兩種或更多種前驅體，而反應物氣體可包含兩種或更多種反應物氣體。前驅體係化學吸附於基板上的氣體且通常含有構成介電膜之基質之主要結構的類金屬或金屬元素，而用於沉積的反應物氣體係當氣體經激發以將原子層或單層固定於基板上時與化學吸附於基板上之前驅體反應的氣體。「化學吸附」係指化學飽和吸附。可使用除製程氣體外之氣體(即，非通過噴淋頭引入之氣體)來(例如)密封反應空間，該氣體包括諸如稀有氣體之密封氣體。在一些具體例中，「膜」指用以覆蓋整個目標或所關注表面，實質上無針孔地在垂直於厚度方向之方向上連續地延伸之層，或簡單地，覆蓋目標或所關注表面之層。在一些具體例中，「層」指形成於表面上的具有特定厚度之結構，或膜之同義詞或非膜結構。膜或層可由具有特定特性之離散單一膜或層或多個膜或層構成，且相鄰膜或層之間的邊界可以或可不清晰且可基於相鄰膜或層之物理、化學及/或任何其他特性、形成製程或順序及/或功能或用途而確定。
此外，在本揭示中，除非另外指明，否則冠詞「一」係指一個物種或包括多個物種之屬。在一些具體例中，術語「由......構成」及「具有」獨立地指「通常或廣泛地包含」、「包含」、「基本上由......組成」或「由......組成」。此外，在本揭示中，在一些具體例中，任何已定義之意義未必排除一般及慣用意義。
此外，在本揭示中，變數之任何兩個數目可構成變數之可工作範圍，此係因為可工作範圍可基於例行工作而判定，且所指示之任何範圍可包括 或排除端點。另外，所指示的變數之任何值(不管該等值是否用「約」指示)可指精確值或近似值且包括等效值，且在一些具體例中可指平均值、中值、代表值、多數值等。
在本揭示中未規定條件及/或結構之處，熟悉本技藝者可鑒於本揭示按常規實驗容易地提供此等條件及/或結構。在所有已揭示具體例中，於一具體例所使用之任何元件可由與其等效的任何元件替換，包括用於預期目的而在本文中明確地、必須地或固有地揭示之彼等元件。此外，本發明同樣可適用於設備及方法。
將針對各種態樣中之較佳具體例來解說該等具體例。然而，本發明不限於該等較佳具體例。
一些具體例係關於一種形成用於間隔件界定圖案化之間隔件的方法，其步驟包括(i)將圖案轉移膜沉積於具有藉由形成於下伏層上之心軸圖案化之表面的模板上，(ii)乾式蝕刻其整個上表面覆蓋有圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之圖案轉移膜的頂部部分及形成於下伏層上之圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下形成於心軸側壁上之圖案轉移膜的側壁部分作為間隔件，及(iii)乾式蝕刻該核心材料，從而形成閒置空間，藉此該模板具有藉由下伏層上之間隔件圖案化的表面，該等間隔件以第一傾斜角朝閒置空間向內傾斜，該第一傾斜角係定義為參考垂直於閒置空間底部之線所測得之各側壁部分之內面的角度，其中傾斜角為零代表完全垂直及傾斜角為正值代表向內傾斜。
於上述，改良處包括：在步驟(i)中，沉積在深度方向中具有不同膜應力之仿形圖案轉移膜作為圖案轉移膜，其中仿形圖案轉移膜之下半部具有第一膜應力及仿形圖案轉移膜之上半部具有第二膜應力，其中該第一膜應力較該第二膜應力更具壓縮性，藉此在步驟(iii)中，該等間隔件以小於第一傾斜角之 第二傾斜角朝閒置空間較小程度地向內傾斜。圖案轉移膜之下半部及上半部構成雙層膜。
在本揭示中，「雙層」膜或間隔件可指具有雙層結構之膜或間隔件，其中當在數學上、地理上、或實質地將結構於厚度(或深度)方向中分割成下半部及上半部時，各作為整體的下及上半部在物理、化學、及/或任何其他特徵或性質、組成或材料、及/或形成製程中具有差異，其中(a)該等差異在形成於包括在下及上半部中之兩個相鄰離散層間形成的離散(或可偵測)邊界(或界面)處不連續地表現於厚度方向中，其中該離散邊界存在於下半部或上半部中或在下及上半部間的實質邊界處；(b)該等差異沒有離散(或可偵測)邊界(或界面)地連續地表現在厚度方向中，其中該等物理、化學、及/或任何其他特徵或性質、組成或材料、及/或形成製程在厚度方向中逐漸地(實質上無不連續點)改變；或(c)該等差異以(a)及(b)中所述之方式以任何組合表現於厚度方向中。在一些具體例中，雙層結構係由滿足(a)的兩個離散層構成，其中該離散邊界存在於下半部或上半部中或在下及上半部間的實質邊界處，其中各層可由滿足以上(a)、(b)、或(c)之單一層或多個層構成。在一些具體例中，雙層膜可由兩個單一膜組成。片語「由...組成」表示不包括未引述的組件。然而，「由...組成」並不排除與本發明無關的額外組件，諸如一般與其相關聯的天然氧化膜。雙層膜可與其他膜接觸。然而，該其他膜不構成雙層膜之一部分，乃因該其他膜不構成垂直間隔件的一部分。
在本揭示中，術語「仿形」一般可指當將圖案轉移膜沉積於心軸上以沿心軸側壁形成膜時，在小區域內之方向間保持正確的角度，例如，維持在心軸(核心材料)之轉角處的角度，不管沉積於心軸頂部上之膜的厚度為何，該膜沿側壁具有實質上均勻的厚度。在一些具體例中，「仿形」係指在沉積於側壁上之中心處之膜厚度對在沉積於頂部上之中心處之膜厚度的比接近1(例如，1±0.2或以下)，其指示沿心軸之側壁形成膜，該膜沿側壁具有實質上均勻的厚度 (「實質上均勻」係指最大差異小於20%或以下或10%或以下)。
在一些具體例中，仿形圖案轉移膜係由多個層(例如，2至6個離散層)構成。
在一些具體例中，多個層係由第一層及沉積於第一層上之第二層構成，其中該第一層之膜應力較第二層之膜應力更具壓縮性，且該第一層具有第一及第二層之總厚度之25%至75%(例如，40%至65%)的厚度。可設定第一及第二層之厚度來調整該等層的最終傾斜角。換言之，由於較厚的層不易彎曲且亦會於其他層上施加更大的變形力，因此層的厚度愈大，該層的變形力就變得愈高。舉例來說，傾斜角之變化可藉由使用以下因數改變S1、T1、S2、及T2(其中S1及T1分別係第一層之膜應力及厚度，而S2及T2分別係第二層之膜應力及厚度：F=(S1-S2)x(T1 x T2)/(T1+T2)3 (1)
舉例來說，當T1/T2=4/6時，可估計得傾斜角與當T1/T2=5/5時相比減小4%(即，[(5x5)/(5+5)3-(4x6)/(4+6)3]/[(5x5)/(5+5)3]=0.04)。類似地，當T1/T2=3/7、2/8、及1/9時，可估計得傾斜角與當T1/T2=5/5時相比分別減小16%、36%、及64%。因此，當T1/T2大約為4/6或更大但小於5/5時，預期傾斜角與當T1/T2=5/5時實質上相同。另一方面，當T1/T2大約為2/8或更小時，預期傾斜角顯著地小於T1/T2=5/5之情況。因此，當使用具有不同膜應力值之多個層時，最終傾斜角可藉由改變各層之厚度來調整。
以上方程式(1)可如下導出。圖18係當間隔件係由多個層構成時(層數係n)，用來解說垂直間隔件之力學之垂直間隔件的示意性圖式。圖19係當間隔件係由兩個層構成時，用來解說垂直間隔件之力學之垂直間隔件的示意性圖式。如圖18中所說明，假定形成於基板110上之間隔件111係由n個層(n係一整數)構成，其中X-軸係設定於層的厚度方向中。當間隔件111向內傾斜時，藉由傾 斜在厚度x處賦予間隔件的應力σL(參照設定於厚度x處之邊界，內層經壓縮，而外層經拉伸)可表示為σL=ax+b(a、b係常數；特定而言，a係與傾斜角成正比)。由間隔件之材料所產生之應力σC可表示為σC=σ1(0<x<t1)、σ2(t1<x<t2)、...、σn(tn-1<x<t)。於厚度x處之應力σ(x)係以上兩分量(即，σL(x)及σC(x))的總和。因此，於厚度x處之位能W(x)可表示為W(x)
Figure 107140247-A0202-12-0010-31
{σL(x)+σC(x)}2。就整個間隔件而言，位能W總和可經由將以上相對於x積分為W總和=ʃ0 tW(x)dx
Figure 107140247-A0202-12-0010-33
ʃ0 t{σL(x)+σC(x)}2dx而獲得。位能具有一最小值，即，W總和(a,b)=最小值。因此，可獲得以下的聯立方程式，及經由解該等方程式，可估計a、b、及傾斜角之值：
Figure 107140247-A0202-12-0010-34
於上述，當間隔件係如圖19中說明由兩個層構成時，得出如下之聯立方程式(2)的解：a=6(σ1-σ2)(t-t1)(t1/t3) (3)
方程式(1)係與方程式(3)相同，其中T1=t1，(T1+T2)=t，SS1=σ1，S2=σ2，及F=a/6。根據方程式(1)或(3)，在其中間隔件係由具有不同應力值之兩個層所構成，且總厚度係恆定的組態中，當層A之厚度對層B之厚度的比係1/1時，參照於由單一層所構成之間隔件之傾斜角的傾斜角差異成為最大，及當該比不為1/1時，由兩個層所構成之間隔件的傾斜角變得較接近由單一層所構成之間隔件的傾斜角，其中間隔件的最終傾斜角可基於如上所論述之方程式(1)的「F」來估計。
在一些具體例中，第一層之厚度係等於或大於第二層之厚度。圖案轉移膜之總厚度可視微影術之解析度、間隔件的預期應用等而寬廣地改變，且通常可在大約3nm至大約40nm之範圍內(更通常為大約10nm至大約40nm)。根據非限制性理論，經由將第一層之厚度設定為等於或大於第二層之厚度，同時間隔件之內層(內層)的頂部較間隔件之外層(第二層)更易被來自電漿之離子轟 擊蝕刻，外層之頂部亦經由內層的經蝕刻表面照射經反射的離子輻照，從而促進外層頂部的蝕刻及增進間隔件頂部的平坦化。
在一些具體例中，仿形圖案轉移膜具有在深度方向中改變的膜應力，其中該膜應力係在向外方向中逐漸或連續地增加。膜應力的逐漸或連續增加可使用於圖案轉移膜之橫截面圖中繪製之近似直線或曲線(可存在局部不連續點)來確定。在一些具體例中，可於圖案轉移膜的整個厚度中觀察到膜應力的逐漸或連續增加。在一些具體例中，膜應力的逐漸增加係逐步增加(於厚度方向中間歇增加)。以上，圖案轉移膜可由具有相同組成的單一離散膜或具有不同組成的多個不同離散膜構成。
在一些具體例中，第一層之膜應力與第二層之膜應力之間的差異係介於大約150MPa與大約800MPa之間(例如，大約200MPa至大約600MPa)。
在一些具體例中，第一及第二層係獨立地由諸如氧化矽、氮化矽、碳化矽、氧化鈦、及氮化鈦等的任何適宜材料構成。氧化矽之特徵主要在於Si-O鍵，但亦可包含碳原子、氫原子、及其他非實質組分諸如與沉積製程相關聯之無可避免的雜質，及氮化矽之特徵主要在於Si-N鍵，但亦可包含碳原子、氫原子、及其他非實質組分諸如與沉積製程相關聯之無可避免的雜質。在一些具體例中，第一及第二層係由不同組成構成；例如，第一層係由氮化矽構成及第二層係氧化矽。在一些具體例中，第一及第二層係由諸如氧化矽的相同組成構成。
各圖案轉移膜之膜應力可經由操控沉積條件來調整。舉例來說，關於氧化矽膜，經由插入n次(n係一整數)子循環(其中使模板暴露至無氧的氬電漿)，在其中通常使模板暴露至氧-氬電漿一次之PEALD的一個循環中，可調整膜應力。舉例來說，關於氮化矽膜，經由改變於PEALD之一個循環中RF功率脈衝的持續時間及/或施加的RF功率，可調整膜應力。經由操控以上參數，可將膜應 力調整為恆定或在厚度方向中逐步或連續地改變。
在一些具體例中，第二傾斜角係在大約-1度至大約1度之範圍內(在其他具體例中，在大約-1度至大約2度之範圍內)。傾斜角係定義為在橫截面圖中代表間隔件之側壁部分之內面之線與在橫截面圖中垂直於代表閒置空間之底面之線的線間之交點處形成的角度。代表內面的線係代表在橫截面圖中通過交點之內面的近似直線。代表底面的線係代表在橫截面圖中通過交點之底面的近似直線。當傾斜角為零時，間隔件的內面完全垂直於底面，當傾斜角為正值時，間隔件的內面向內傾斜，及當傾斜角為負值時，間隔件的內面向外傾斜。
在一些具體例中，多個層係藉由電漿增強型原子層沉積(PEALD)來沉積，其能夠沉積高度仿形膜(例如，80%或更高或90%或更高的仿形性)。
在一些具體例中，第一層具有較第二層低的抗乾式蝕刻性。藉由操控第一及第二層的抗乾式蝕刻性，可調整垂直間隔件的頂部輪廓。在一些具體例中，第一層與第二層間之抗乾式蝕刻性的差異係使得在(乾式蝕刻模板的)步驟(ii)(其係回蝕製程)中，各間隔件之頂部藉由抑制間隔件因乾式蝕刻引起的肩部損失而變得實質上平坦。抗乾式蝕刻性係指在使用電漿之回蝕製程期間，間隔件材料多快速或多緩慢地被蝕刻(即，乾式蝕刻速率)。在一些具體例中，第一與第二層間之乾式蝕刻速率的差異係在大約0.05nm/秒至大約0.5nm/秒之範圍內，通常大約0.1nm/秒至0.3nm/秒，以有效地使垂直間隔件的頂部變平坦。在一些具體例中，關於利用電漿的回蝕製程(步驟(ii))，使用諸如CF4、CHF3、或C4F8之含氟蝕刻劑與氬的組合(用來蝕刻氮化矽，額外地氧)，而關於利用電漿的剝除製程(灰化製程)(步驟(iii))，使用氧或氬氣作為蝕刻劑。為蝕刻由氧化矽外層及氮化矽內層所構成的圖案轉移膜，首先，在針對蝕刻氧化矽所設定的條件下蝕刻氧化矽外層，然後在針對自心軸頂部移除氧化矽外層所設定之時段後，在針對蝕刻氮化矽所設定的條件下蝕刻氮化矽內層。在一些具體例中，在剝除製程期 間，垂直間隔件之頂部的平坦化係連續地進行。
在另一態樣中，一些具體例係關於一種形成用於間隔件界定圖案化之間隔件的方法，其步驟包括(i)將圖案轉移膜沉積於具有藉由形成於下伏層上之心軸圖案化之表面的模板上，(ii)乾式蝕刻其整個上表面覆蓋有圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之圖案轉移膜的頂部部分及形成於下伏層上之圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下形成於心軸側壁上之圖案轉移膜的側壁部分作為間隔件，及(iii)乾式蝕刻該核心材料，從而形成閒置空間，藉此該模板具有藉由下伏層上之間隔件圖案化的表面，該等間隔件以第一傾斜角遠離彼此向外傾斜，該第一傾斜角係定義為參考垂直於閒置空間底部之線所測得之各側壁部分之內面的角度，其中傾斜角為零代表完全垂直及傾斜角為負值代表向外傾斜。
於上述，改良處包括：在步驟(i)中，沉積在深度方向中具有不同膜應力之仿形圖案轉移膜作為圖案轉移膜，其中仿形圖案轉移膜之下半部具有第一膜應力及仿形圖案轉移膜之上半部具有第二膜應力，其中該第一膜應力較該第二膜應力更具拉伸性，藉此在步驟(iii)中，該等間隔件以大於第一傾斜角之傾斜角遠離彼此較小程度地向外傾斜。當垂直間隔件傾向於在減小傾斜角之方向中向外傾斜時，文中揭示之具體例亦可適用，藉此形成具有實質上零(例如，±1度)之傾斜角的垂直間隔件。
在又另一態樣中，一些具體例係關於一種形成用於間隔件界定多重圖案化之垂直間隔件的方法，其包括：(i)在反應空間中提供具有藉由形成於下伏層上之心軸圖案化之表面的模板；(ii)沉積具有第一膜應力之第一仿形圖案轉移膜，及將具有第二膜應力之第二仿形圖案轉移膜連續地沉積於模板的整個圖案化表面上，其中該第一及該第二膜應力不同；(iii)乾式蝕刻其整個上表面覆蓋有第一及第二圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之 第一及第二圖案轉移膜的一部分及第一及第二圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下第一及第二圖案轉移膜的垂直部分作為垂直間隔件；及(iv)乾式蝕刻該核心材料，從而在垂直間隔件之間形成閒置空間，藉此該模板具有藉由下伏層上之垂直間隔件圖案化的表面。
在一些具體例中，以上方法進一步包括：(v)測量垂直間隔件的傾斜角，其係定義為參考垂直於閒置空間底部之線所測得之面向閒置空間之垂直間隔件之內面的角度，其中傾斜角為零代表完全垂直及傾斜角為正值代表向內傾斜，隨後判定傾斜角是否在目標範圍內；(vi)再次進行步驟(i)至(iv)：(a)如傾斜角在目標範圍內，則不進行改變來形成最終垂直間隔件；(b)如傾斜角大於目標範圍，則進行改變，其中沉積具有較第一膜應力高出一可測量程度之壓縮應力的仿形圖案轉移膜來作為步驟(ii)中之第一仿形圖案轉移膜，及/或沉積具有較第二膜應力高出一可測量程度之拉伸應力的仿形圖案轉移膜來作為步驟(ii)中之第二仿形圖案轉移膜；或(c)如傾斜角小於目標範圍，則進行改變，其中沉積具有較第一膜應力低至一可測量程度之壓縮應力的仿形圖案轉移膜來作為步驟(ii)中之第一仿形圖案轉移膜，及/或沉積具有較第二膜應力低至一可測量程度之拉伸應力的仿形圖案轉移膜來作為步驟(ii)中之第二仿形圖案轉移膜；及(vii)如進行步驟(vi)中之(b)或(c)，則於增加(b)或(c)中所使用之可測量程度後，重複步驟(v)及(vi)。通過此等步驟，可有效地形成具有期望或目標傾斜角的垂直間隔件。
在一些具體例中，第一仿形圖案轉移膜具有第一抗乾式蝕刻性，及第二仿形圖案轉移膜具有第二抗乾式蝕刻性；及步驟(v)進一步包括判定垂直間隔件之頂部是否實質上平坦，其中如垂直間隔件之頂部並非實質上平坦，則：在步驟(vi)中，沉積具有較第一抗乾式蝕刻性以及較第二仿形圖案轉移膜低至一可測量程度之抗乾式蝕刻性的第一仿形圖案轉移膜來作為第一仿形圖案轉移膜，及/或沉積具有較第二抗乾式蝕刻性以及較第一仿形圖案轉移膜高出一可測 量程度之抗乾式蝕刻性的第二仿形圖案轉移膜來作為第二仿形圖案轉移膜；及在步驟(vii)中，於增加該可測量程度後重複步驟(v)及(vi)，直至垂直間隔件之頂部實質上平坦為止。因此，可有效地形成不僅具有期望的傾斜角，並且亦具有實質上平坦頂部的垂直間隔件。
在本揭示中，間隔件之「實質上平坦的」頂部可指頂部彎曲或傾斜部分之高度大約為10nm或以下，或替代地或另外地，小於間隔件高度之20%(較佳10%或以下)的頂部(參見圖11)。
在又另一態樣中，一些具體例係關於一種形成用於間隔件界定圖案化之間隔件的方法，其步驟包括(i)將圖案轉移膜沉積於具有藉由形成於下伏層上之心軸圖案化之表面的模板上，(ii)乾式蝕刻其整個上表面覆蓋有圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之圖案轉移膜的頂部部分及形成於下伏層上之圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下形成於心軸側壁上之圖案轉移膜的側壁部分作為間隔件，及(iii)乾式蝕刻該核心材料，從而形成閒置空間，藉此該模板具有藉由下伏層上之間隔件圖案化的表面，其中面向閒置空間之各間隔件的肩部部分(該肩部部分係間隔件頂部的外部轉角)經損失或蝕刻，從而形成自間隔件頂部之外側至內側的傾斜表面。
於上述，改良處包括：在步驟(i)中，沉積由包括第一層及沉積於第一層上之第二層之雙層膜構成的仿形圖案轉移膜作為圖案轉移膜，其中該第一層具有較該第二層低的抗乾式蝕刻性，其中第一層與第二層間之抗乾式蝕刻性的差異係使得在步驟(iii)中，各間隔件之頂部藉由抑制間隔件因乾式蝕刻引起的肩部損失而變得實質上平坦。因此，可有效地形成具有實質上平坦頂部的間隔件。
在一些具體例中，第一層係由氮化矽構成，及第二層係由氧化矽構成。
將參看圖式解說具體例。然而，本發明不限於該等圖式。
圖2係說明根據本發明之一具體例製造垂直間隔件結構之步驟的流程圖。在步驟(i)中，於反應空間中提供具有藉由形成於下伏層上之心軸圖案化之表面的模板。心軸的圖案可係藉由光微影術使用習知之UV光或極UV光形成。心軸係由有機光阻劑材料製成。
在步驟(ii)中，於模板的整個圖案化表面上沉積具有第一膜應力之第一仿形圖案轉移膜，及連續地沉積具有第二膜應力之第二仿形圖案轉移膜，其中該等第一及第二膜應力不同。通常，仿形圖案轉移膜係藉由諸如PEALD、熱ALD之ALD、或任何等效沉積方法來形成。
在步驟(iii)中，乾式蝕刻其整個上表面覆蓋有第一及第二圖案轉移膜的模板，藉此選擇性地移除形成於心軸頂部上之第一及第二圖案轉移膜的一部分及第一及第二圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下第一及第二圖案轉移膜的垂直部分作為垂直間隔件。此步驟亦稱為回蝕。乾式蝕刻通常係使用電漿使用針對目標膜之組成或材料選擇的適當蝕刻劑氣體來進行。較佳地，電漿蝕刻使用電容式耦合電漿或直接電漿，乃因該種電漿除自由基外亦包含離子，而遠端電漿則實質上沒有離子。此外，該種電漿通常係各向異性且適用於圖案化。
在步驟(iv)中，乾式蝕刻核心材料，從而在垂直間隔件之間形成閒置空間，藉此該模板具有藉由下伏層上之垂直間隔件圖案化的表面。此步驟亦稱為灰化或剝除。蝕刻劑氣體係針對待移除的組成或材料來選擇。
圖3係說明根據本發明之另一具體例調整垂直間隔件結構形狀之步驟的流程圖，其可在根據圖2中說明之流程圖獲得之膜輪廓不令人滿意(通常就間隔件的垂直程度而言)時進行。在步驟(v)中，測量垂直間隔件的傾斜角，隨後在步驟D1中判定傾斜角是否係在目標範圍內。圖7說明傾斜角。圖7係根據本發 明之一具體例製造於基板上之間隔件之橫截面圖的STEM(掃描式穿透電子顯微鏡)照片，該照片係用來顯示傾斜角。如圖7中所說明，傾斜角θ係定義為面向閒置空間110之垂直間隔件104之內面104a參考垂直於閒置空間110之底部102之底面102a之線所測得之角度，其中傾斜角為零代表完全垂直及傾斜角θ為正值代表向內傾斜，而傾斜角θ為負值代表向外傾斜。
在步驟D1中，判定傾斜角是否係在目標範圍內。如判定傾斜角係在目標範圍內，則在步驟(vi)(a)中，不作改變地再次進行步驟(i)至(iv)來形成最終的垂直間隔件，即製程結束。
在步驟D1中，如判定傾斜角不落在目標範圍內且係大於目標範圍，則在步驟(vi)(b)中，在改變下再次進行步驟(i)至(iv)，其中沉積具有較第一膜應力高出一可測量程度之壓縮應力的仿形圖案轉移膜來作為步驟(ii)中之第一仿形圖案轉移膜，及/或沉積具有較第二膜應力高出一可測量程度之拉伸應力的仿形圖案轉移膜來作為步驟(ii)中之第二仿形圖案轉移膜。
在步驟D1中，如判定傾斜角不落在目標範圍內且係小於目標範圍，如傾斜角係小於預設範圍，則在步驟(vi)(c)中，在改變下再次進行步驟(i)至(iv)，其中沉積具有較第一膜應力低至一可測量程度之壓縮應力的仿形圖案轉移膜來作為步驟(ii)中之第一仿形圖案轉移膜，及/或沉積具有較第二膜應力低至一可測量程度之拉伸應力的仿形圖案轉移膜來作為步驟(ii)中之第二仿形圖案轉移膜。
在步驟(vi)(b)或步驟(vi)(c)後的步驟中，於增加在步驟(vi)(b)或步驟(vi)(c)中所使用之可測量程度後，製程回到步驟(v)及(vi)。
步驟D2及步驟(vii)係使得間隔件之頂部能夠實質上平坦的額外或可選步驟(該額外、可選、或替代的流程以虛線指示)。在步驟D2中，判定垂直間隔件之頂部是否實質上平坦。如判定垂直間隔件之頂部非實質上平坦，則在 步驟(vii)中，沉積具有較第一抗乾式蝕刻性以及較第二仿形圖案轉移膜低至一可測量程度之抗乾式蝕刻性的第一仿形圖案轉移膜來作為第一仿形圖案轉移膜，及/或沉積具有較第二抗乾式蝕刻性以及較第一仿形圖案轉移膜高出一可測量程度之抗乾式蝕刻性的第二仿形圖案轉移膜來作為第二仿形圖案轉移膜，及於增加該可測量程度以不僅調整傾斜角，而且亦調整垂直間隔件之頂部輪廓後，製程移至步驟(vi)(b)或步驟(vi)(c)。
在一些具體例中，調整垂直間隔件之頂部輪廓可與調整垂直間隔件之傾斜角獨立地進行。圖15係說明根據本發明之另一具體例調整垂直間隔件結構之頂部輪廓之步驟的流程圖。在步驟(1)中，評估垂直間隔件的頂部輪廓。在步驟(2)中，判定間隔件之頂部是否實質上平坦。如判定間隔件之頂部實質上平坦，則在步驟(3)中，製程回到圖2之流程圖中所說明的步驟(i)至(iv)，未對圖案轉移膜進行改變，而形成最終的垂直間隔件。如判定間隔件之頂部非實質上平坦，則在步驟(4)中，製備具有較第一圖案轉移膜高之乾式蝕刻速率(DER)的圖案轉移膜作為第一圖案轉移膜，及/或製備具有較第二圖案轉移膜低之DER的圖案轉移膜作為第二圖案轉移膜。在步驟(5)中，製程回到圖2之流程圖中所說明的步驟(i)至(iv)，形成經修改的圖案轉移膜，及隨後，製程回到步驟(1)。
根據以上論述的流程圖，可於間隔件界定雙重圖案化(SDDP)中形成如圖5及6中所說明之垂直間隔件。圖5係根據本發明之一具體例之雙重圖案化(步驟(a)至(c))的示意性圖式。在步驟(a)中，將心軸(光阻劑)101圖案化作為下伏層102上之核心材料。在步驟(b)中，沉積包含第一層105a及第二層105b之圖案轉移膜105以覆蓋心軸101之經暴露表面及下伏表面102之經暴露表面的全體。在步驟(c)中，經由乾式蝕刻，蝕刻膜105及心軸101之水平部分，而形成由內層106a(第一層105a)及外層106b(第二層105b)所構成的間隔件106。經由使用以上製程，於步驟(c)中由間隔件106所構成的圖案可具有步驟(a)中之光阻劑101之圖案 之一半的間距，即可實現雙倍密度間距圖案化。在此製程中，如於本揭示中所論述，由於間隔件106係由雙層圖案轉移膜105形成，因此可藉由使用第一及第二層間之膜應力的差異來調整間隔件的傾斜角，藉此形成具有實質上零之傾斜角的間隔件(如圖4所示在核心剝除步驟(c)期間或之後不朝向閒置空間110傾斜)。可有效地抑制傾斜現象以使半導體製造商可容易地精確且連續地進行隨後的積體製程。預期以上特徵將隨技術進步及小型化進展而變得更為重要。
圖6係根據本發明之另一具體例之雙重圖案化(步驟(a)至(c))的示意性圖式。在步驟(a)中，將心軸(光阻劑)101圖案化作為下伏層102上之核心材料。在步驟(b)中，沉積包含第一層107a及第二層107b之圖案轉移膜107以覆蓋心軸101之經暴露表面及下伏表面102之經暴露表面的全體。第一層107a具有較第二層107b高的乾式蝕刻速率。在步驟(c)中，藉由乾式蝕刻，蝕刻膜107及心軸101之水平部分以形成由內層108a(第一層107a)及外層108b(第二層107b)所構成的間隔件108。藉由使用以上製程，步驟(c)中由間隔件106所構成之圖案可具有步驟(a)中之光阻劑101之圖案之一半的間距，即可實現雙倍密度間距圖案化。在此製程中，如於本揭示中所論述，由於間隔件108係由雙層圖案轉移膜107形成，因此可藉由使用第一及第二層間之乾式蝕刻速率的差異來調整間隔件的頂部輪廓112，藉此使間隔件之頂部部分112變得實質上平坦(如圖4及5所示抑制肩部損失)。可有效地抑制肩部損失現象以使半導體製造商可容易地精確且連續地進行隨後的積體製程。預期以上特徵將隨技術進步及小型化進展而變得更為重要。
在圖6中說明的間隔件中，由於雙層間隔件之頂部邊緣實質上平坦，因此經由在圖6中之步驟(a)中使用間隔件108作為心軸101，及重複步驟(b)及(c)，間隔件不僅可有效且適當地應用至SDDP，而且可應用至間隔件界定四重圖案化(SDQP)或更高層級(間隔件界定多重圖案化，SDMP)。
不欲限制本發明，可如圖12中所說明來解說平坦化機制。圖12 說明形成具有平坦頂部之間隔件的機制，其中(a)示意性地說明用來形成間隔件的雙層膜，及(b)至(f)係顯示根據本發明之一具體例之步驟的放大示意性部分圖。在蝕刻前，形成於基板102上之心軸101經覆蓋圖案轉移膜107之第一層(內層)107a，其又經圖案轉移膜107之第二層(外層)107b覆蓋，如(a)中所說明。在此實例中，內層107a係由氮化矽構成，而外層107b係由氧化矽構成，其中內層107a具有較外層107b高的乾式蝕刻速率。圖案轉移膜107之側壁部分將形成如(b)中所說明之間隔件，其係圖案轉移膜107之上方側壁部分(肩部部分)60的放大圖。首先，肩部部分的外層107b主要藉由含離子的電漿各向異性地蝕刻，藉此使肩部部分處的內層107a暴露出來，其中內層107a的經蝕刻表面107a1及外層107b的經蝕刻表面107b1係如(c)中所說明般暴露出來。由於肩部部分60渾圓，因此經由各向異性蝕刻所形成的經暴露表面如(c)中所說明自然地傾斜。隨著各向異性蝕刻進行(在此實例中蝕刻條件自主要針對蝕刻氮化矽設定的條件轉變為主要針對蝕刻氧化矽設定的條件)，由於內層107a具有較外層107b高的乾式蝕刻速率，因而內層107a之經暴露表面107a1較外層107b的經暴露表面107b1經離子轟擊或來自電漿之離子照射蝕刻地更多，藉此形成如(d)中所說明之內層107a之經暴露表面107a2及外層107b之經暴露表面107b2及經暴露表面107b3。外層107b之經暴露表面107b3係由於內層107a與外層107b間之蝕刻速度的差異而形成，其中內層107a較外層107b更快速地被蝕刻，藉此於內層107a與外層107b之間形成階梯(錐狀突起)。由於經暴露表面107a2傾斜且離子轟擊於經暴露表面107a2上朝向經暴露表面107b3反射(如(d)中之箭頭所說明)，因此經暴露表面107b3接受經反射離子，且錐狀突起自其尖端被經反射離子蝕刻。隨著各向異性蝕刻進一步進行，藉由經暴露表面107a3反射之離子繼續轟擊錐狀突起，藉此如(e)中所說明降低錐狀突起之高度，其中以虛線指示的部分107b5經移除，藉此形成經暴露表面107b4。隨著各向異性蝕刻進一步進行，突起的高度降低，且經暴露表面107a4及經暴露表 面107b6如(f)中所說明導致形成實質上平坦的表面。
文中揭示的雙層膜可用於包括間隔件界定雙重圖案化(SDDP)的多種應用中。圖14係根據本發明之一具體例使用SDDP之圖案轉移及目標蝕刻的示意性圖式，其中使用雙層膜作為圖案轉移膜來將圖案自第一模板轉移至第二模板。使用抗反射層(ARL)94作為用來提高SDDP製程中之圖案密度(例如，間距減小)的第一模板。使用蝕刻硬遮罩82作為用來蝕刻目標層81的第二模板。在圖14之步驟(a)中，於抗反射層94(由，例如，非晶形碳所構成)上形成光阻劑圖案93(由，例如，酚醛清漆(Novolacs)所構成，使得抗反射層94可於步驟(b)中以光阻劑圖案蝕刻，該步驟(b)為將圖案轉移至第一模板94之步驟。在步驟(c)中，根據任何所揭示之具體例或其之等效具體例沉積雙層膜95(作為圖案轉移膜)，隨後在步驟(d)(其係間隔件RIE(反應性離子蝕刻)步驟)中蝕刻。藉由剝除抗反射層94之材料(於核心部分96中之光阻劑材料)，於步驟(e)中形成垂直間隔件84。由於雙層膜95具有高蝕刻選擇性，因此用來於其上形成間隔件之抗反射層94(第一模板)可係薄的，且雙層膜可於蝕刻期間保留而於步驟(e)中形成垂直間隔件84。在一些具體例中，抗反射層之厚度係約5至50nm(通常10至30nm)，及雙層膜之厚度係約5至50nm(通常10至20nm)。在步驟(f)中，藉由蝕刻將圖案自垂直間隔件84轉移至第二模板82而形成第二垂直間隔件74，及在步驟(g)中，將第一垂直間隔件84(雙層間隔件)剝除。由於雙層間隔件84之頂部邊緣係平坦的，因此可準確地完成藉由第二垂直間隔件74形成第二模板82。在步驟(h)中，使用第二垂直間隔件74使形成於矽基板70上之目標層81進行乾式蝕刻。在步驟(i)中，將第二垂直間隔件74剝除。在一些具體例中，抗反射層、蝕刻硬遮罩、雙層膜(間隔件)、及目標層可藉由文中揭示之任何方法或其等效方法或藉由脈衝PECVD或PEALD來沉積。
雙層膜不僅抗HCl、及TMAH濕式蝕刻，而且亦例如，抗BCl3、 BCl3/Ar乾式蝕刻，且因此，在步驟(f)中，當將圖案轉移至第二模板82時，雙層84保留圖案。另一方面，雙層膜對氧化、濕式蝕刻化學與氧化及HF(常用於半導體加工中)交替之組合、或(例如)基於氧或CF4之乾式蝕刻敏感，因此，在步驟(g)中，雙層間隔件84可有效地經剝除。
可藉由操控諸如RF功率、RF功率脈衝之持續時間、反應物之流動速率、額外進行之子循環的數目或重組循環等的沉積參數來形成具有不同膜應力的圖案轉移膜。熟悉技藝人士可鑑於本揭示根據例行實驗輕易地確定該等沉積參數。
關於用作圖案轉移膜之第一及/或第二層的氧化矽膜，例如，藉由操控反應物之進給，可調整所得氧化矽膜的膜應力。圖16說明根據本發明之一具體例在沉積具有不同膜應力之氧化矽膜之一個循環中的製程順序，其中該一個循環係由循環A及循環B所構成。在此具體例中，循環A係主要循環，而循環B係子循環(次要循環)。兩循環皆包含「進料」，其中將Si前驅體饋送至反應空間，使得前驅體吸附或化學吸附於模板表面上；「沖洗」，其中沖洗反應空間，使得將未經吸附或化學吸附之過量前驅體自模板表面移除；「RF」，其中向反應空間施加RF功率，使得經吸附或化學吸附之前驅體暴露至電漿，從而形成原子層；及「沖洗」，其中沖洗反應空間，使得將未反應組分及副產物自模板表面移除。使用在整個循環中恆定且連續供應至反應空間的載氣流動來將前驅體供應至反應空間。在循環A中，在整個循環A中將氧恆定且連續地供應至反應空間(以產生氧-氬電漿)，而在循環B中，在整個循環B中未將氧供應至反應空間(以產生氬電漿)。此外，循環B中之RF功率可高於循環A中者，及/或循環B中之RF功率脈衝之持續時間可較循環A中者長。於進行循環A一次後，進行循環B n次(n係0至10之整數，例如，1至5)。經由改變循環B的重複次數(n)，可於壓縮方向中改變所得氧化矽膜的膜應力。另外或替代地，經由於循環A中改變RF功率 及/或RF功率脈衝之持續時間，亦可調整氧化矽膜的膜應力。在一些具體例中，可於大約+100MPa至大約-300MPa、較佳大約0MPa至大約-200MPa之範圍內改變氧化矽膜的膜應力。
可例如經由改變反應物氣體之流動速率與稀釋氣體之流動速率的比來調整氧化矽的乾式蝕刻速率。在一些具體例中，取決於乾式蝕刻條件，可於大約0.7nm/秒至大約1.5nm/秒、較佳大約0.5nm/秒至大約1.0nm/秒之範圍內改變氧化矽的乾式蝕刻速率。
為沉積氧化矽膜，BDEAS(雙-二乙胺基矽烷)、3DMAS(叁(二甲胺基)矽烷)、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為前驅體。Ar、He、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為載氣及稀釋氣體中之各者。O2、N2O、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為反應物氣體。
在一些具體例中，氧化矽膜之沉積循環可藉由PEALD使用圖16中說明之製程順序來進行，其之一個循環係在下表1中顯示的條件下進行。
Figure 107140247-A0202-12-0024-1
於上述，針對其他尺寸的基板，可應用自以上計算得之每cm2的瓦數。
關於用作圖案轉移膜之第一及/或第二層的氮化矽膜，例如，經由操控反應物之進料，可調整所得氮化矽膜的膜應力。圖17說明根據本發明之一具體例在沉積具有不同膜應力之氮化矽膜之一個循環中的製程順序。在此具體例中，循環包含「進料」，其中將Si前驅體饋送至反應空間，使得前驅體吸附 或化學吸附於模板表面上；「沖洗1」，其中沖洗反應空間，使得將未經吸附或化學吸附之過量前驅體自模板表面移除；「RF」，其中向反應空間施加RF功率，使得經吸附或化學吸附之前驅體暴露至電漿，從而形成原子層；及「沖洗2」，其中沖洗反應空間，使得將未反應組分及副產物自模板表面移除。使用在整個循環中恆定且連續供應至反應空間的載氣流動來將前驅體供應至反應空間。在循環中，在整個循環中將Ar及N2恆定且連續地供應至反應空間。經由於循環中改變RF功率及/或RF功率脈衝之持續時間，可調整氮化矽膜的膜應力。舉例來說，經由增加RF功率脈衝的持續時間，可於壓縮方向中改變氮化矽的膜應力。在一些具體例中，氮化矽膜的膜應力可在大約-300MPa至大約-900MPa、較佳大約-400MPa至大約-800MPa之範圍內改變。
氮化矽的乾式蝕刻速率可藉由循環中之RF功率脈衝的持續時間來調整。在一些具體例中，取決於乾式蝕刻條件，氮化矽之乾式蝕刻速率可在大約0.5nm/秒至大約2nm/秒，較佳大約1nm/秒至大約1.5nm/秒之範圍內變化。
為沉積氮化矽膜，BDEAS(雙-二乙胺基矽烷)、DCS(二氯矽烷)、矽烷、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為前驅體。Ar、He、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為載氣及稀釋氣體中之各者。無需使用稀釋氣體且可完全除去(如於以下論述的實施例1中)。N2、H2、NH3、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為反應物氣體。
在一些具體例中，氮化矽膜之沉積循環可藉由PEALD使用圖17中說明之製程順序來進行，其之一個循環係在下表2中顯示的條件下進行。
Figure 107140247-A0202-12-0026-2
於上述，針對其他尺寸的基板，可應用自以上計算得之每cm2的瓦數。
在一些具體例中，氮化矽膜可使用美國專利公開案第2017/0062204 A1號中揭示之方法，特定言之圖4A及4B及公開案的對應內文來沉積，將該案之揭示的全體內容以引用的方式併人本文。
在一些具體例中，氧化矽膜之乾式蝕刻(回蝕製程)係在下表3中顯示的條件下進行。
Figure 107140247-A0202-12-0027-3
於上述，針對其他尺寸的基板，可應用自以上計算得之每cm2的瓦數。
在一些具體例中，SiN膜之乾式蝕刻(回蝕製程)係在下表4中顯示的條件下進行。
Figure 107140247-A0202-12-0027-4
於上述，針對其他尺寸的基板，可應用自以上計算得之每cm2的瓦數。
圖案轉移膜的第一層及第二層可由不同組成物或相同組成物構成，只要第一及第二層間之膜應力的差異經適當調整即可(例如，大約150MPa至大約800MPa、較佳大約200MPa至大約600MPa之差異，亦取決於各層之厚度，其中考慮各層之膜應力及厚度之乘積的差異)，及另外或替代地，只要適當地調整第一及第二層間之乾式蝕刻速率的差異即可(例如，大約0.1nm/秒至大約2nm/秒、較佳大約0.2nm/秒至大約1.5nm/秒之差異，亦取決於共同蝕刻條件)。舉例來說，可有利地選擇以下的組合(第一/第二層)：SiN/SiO、SiO/SiN、SiO/SiO、及SiN/SiN。當第一(內)層係SiN及第二(外)層係SiO時，SiO首先在針對SiO設定之蝕刻條件下蝕刻，及隨後SiN在回蝕步驟期間在心軸之頂部部分上針對SiN設定之蝕刻條件下蝕刻。在以下時刻將蝕刻條件自針對SiO之條件轉變至針對SiN之條件：(i)當在心軸之頂部部分之SiO層的一部分變薄或幾乎暴露出來時，(ii)當在心軸之頂部部分之SiO層的一部分或大部分(除了SiO層之側壁的頂部部分外)被移除且SiN膜於心軸之頂部部分暴露出來時，或(iii)在以上(i)與(ii)之間的時刻。當在針對SiN設定之蝕刻條件下，SiN層之乾式蝕刻速率高於SiO層之乾式蝕刻速率，可達成圖12中所說明的平坦化效應。
在一些具體例中，核心材料之乾式蝕刻(灰化或剝除製程)係在下表5中顯示的條件下進行。
Figure 107140247-A0202-12-0029-5
於上述，針對其他尺寸的基板，可應用自以上計算得之每cm2的瓦數。
沉積製程、回蝕製程、及灰化製程可於相同反應室或不同反應室中進行。當使用不同反應室時，較佳地，該等室係經由晶圓操縱室與真空機器人連接，使得可避免基板暴露至空氣，且可提高生產量。
製程循環可使用(例如)包括圖1中所說明之設備的任何合適設備執行。圖1為可用於本發明之一些具體例中之PEALD設備(理想地結合下文所描述的經程式設計以進行下述順序之控制項)的示意性視圖。在此圖中，藉由在反應室3之內部11(反應區)中設置彼此平行且面對的一對導電平板電極(電容耦合電極)4、2，施加HRF功率(13.56MHz或27MHz)20至一側，及將另一側12電接地，在該等電極之間激發電漿。一溫度調節器係設置於下部載台2(下部電極)中，且置放於其上之基板1之溫度在給定溫度下保持恆定。上部電極4亦充當噴淋板，且反應氣體(及稀有氣體)及前驅體氣體係分別經由氣體管線21及氣體管線22及經由噴淋板4而引入至反應室3中。另外，在反應室3中，設置了具有排氣管線7之圓管13，經由該排氣管線，反應室3之內部11中之氣體被排出。另外，稀釋氣體係經由氣體管線23引入至反應室3中。另外，安置於反應室3下之轉移室5具備 密封氣體管線24以經由轉移室5之內部16(轉移區)將密封氣體引入至反應室3之內部11，其中設置有用於將反應區與轉移區隔開之分隔板14(自此圖省略閘閥，晶圓係經由該閘閥轉移至轉移室5中或自該轉移室轉移)。該轉移室亦具備排氣管線6。在一些具體例中，多元素膜沉積及表面處理係在同一反應空間中執行，使得所有步驟可連續地進行，而不會將基板暴露於空氣或其他含氧氛圍。在一些具體例中，遠端電漿單元可用於激發氣體。在一些具體例中，可使用切換不活潑氣體之流動與前驅體氣體之流動的系統來在脈衝中引入前驅體氣體，而不使反應室之壓力實質上地波動。
在一些具體例中，可使用雙腔室反應器(用於處理彼此緊密地安置之晶圓的兩個區段或隔室)，其中反應物氣體及稀有氣體可經由共用管線來供應，而前驅體氣體係經由非共用管線來供應。
熟悉技術者應瞭解，該設備包括一或多個控制器(未圖示)，其經程式設計或另外組構以使如本文中別處所描述之沉積及反應器清潔製程進行。如熟悉技術者應瞭解，控制器係與反應器之各種電源、加熱系統、泵、機器人及氣流控制器或閥通信。
參考以下工作實施例來進一步說明本發明。然而，該等實施例不欲限制本發明。在實施例中未規定條件及/或結構之處，熟悉本技藝者可鑒於本揭示內容根據常規實驗容易地提供此等條件及/或結構。此外，特定實施例中所應用之數字可經修改至少±50%之範圍，且在一些具體例中，該等數字為近似值。
實施例
參考實施例1
各藉由PEALD將SiO膜及SiN膜沉積於Si基板(Φ300mm)上，其之一個循環係使用圖1中說明之PEALD設備基於圖16及17中說明之製程順序在下表6及7中顯示的條件(沉積循環)下進行。
於將各基板自反應室取出後，測量各膜的膜應力。結果示於下表8。膜應力係基於在將膜沉積於基板上之前及之後之基板的「彎曲」來測量，其中「彎曲」係以曲率半徑表示，且膜應力係使用史東納(Stoney)方程式來計算。
Figure 107140247-A0202-12-0031-6
Figure 107140247-A0202-12-0032-7
Figure 107140247-A0202-12-0032-8
表8顯示於沉積7天後測量的應力。然而，於沉積後立即測得的應力與沉積7天後者實質上相同，儘管應力隨時間輕微地逐漸改變。該逐漸改變並不明顯，且可能係由膜吸收水分所引起。如表8所示，關於SiO膜，藉由添加循環B，膜應力變得更具壓縮性，及關於SiN膜，藉由延長RF功率脈衝的持續時間，膜應力變得更具壓縮性。
比較實施例1
經由使用於Si基板(Φ300mm)上的圖案化SiARC(含矽抗反射塗層)形成心軸圖案(由非晶形碳製成)來製備模板，其中該圖案化心軸具有90nm之 高度、30nm之寬度、及115nm之間距。於模板上，藉由PEALD在對應於在參考實施例1中描述之針對SiO(n=0)者(具有-10.7之膜應力)之條件下以95%之仿形性沉積具有35nm厚度之SiO膜作為單層圖案轉移膜。圖8中之(a)顯示SiO單層膜之橫截面圖的STEM照片。
接下來，在與沉積製程相同的室中，使SiO單層膜在下表9中顯示之條件下進行回蝕製程，隨後在下表10中顯示之條件下進行灰化製程，從而形成間隔件。注意，表9中顯示之回蝕製程亦蝕刻SiARC膜。
Figure 107140247-A0202-12-0033-9
Figure 107140247-A0202-12-0033-10
圖8中之(c)顯示由SiO單層膜製成之間隔件之橫截面圖的STEM照片。如圖8中之(c)中顯示，間隔件透過核心移除(即灰化製程)朝閒置空間傾斜。經測得間隔件之傾斜角為大約2.2度。
比較實施例2
以與比較實施例1實質上相似的方式製備模板及將SiO膜沉積於其上，除了藉由PEALD在對應於在參考實施例1中描述之針對SiO(n=3)者(具有-169.3之膜應力)之條件下以90%之仿形性沉積具有35nm厚度之SiO膜作為單層圖案轉移膜。圖8中之(b)顯示SiO單層膜之橫截面圖的STEM照片。
接下來，使SiO單層膜及SiARC膜在與比較實施例1中相同的條件下進行回蝕製程，隨後在與比較實施例1中相同的條件下進行灰化製程，從而形成間隔件。圖8中之(d)顯示由SiO單層膜製成之間隔件之橫截面圖的STEM照片。如圖8中之(d)中顯示，間隔件透過核心移除(即灰化製程)朝閒置空間傾斜。經測得間隔件之傾斜角為大約2.9度。
實施例1
以與比較實施例1或2實質上相似的方式製備模板及沉積SiO膜，除了將SiO膜沉積為SiO雙層圖案轉移膜，其係由以與比較實施例1實質上相似之方式沉積之具有20nm厚度之內部SiO單層膜(SiO(n=0))、及以與比較實施例2實質上相似之方式沉積之具有15nm厚度之外部SiO單層膜(SiO(n=3))所構成。該SiO雙層圖案轉移膜具有90%之仿形性。圖9中之(c)顯示SiO雙層膜之橫截面圖的STEM照片。換言之，具有20nm厚度之內層係具有-10.7MPa之應力的SiO單層膜(相對地拉伸性)，而具有15nm厚度之外層係具有-169.3MPa之應力的SiO單層膜(相對地壓縮性)。
接下來，使SiO雙層膜及SiARC膜在與比較實施例1中相同的條件下進行回蝕製程，隨後在與比較實施例1中相同的條件下進行灰化製程，從而形成間隔件。圖9中之(d)顯示由SiO雙層膜製成之間隔件之橫截面圖的STEM照片。如圖9中之(d)中顯示，間隔件透過核心移除(即灰化製程)相較於圖9(a)中顯示之比較實施例1中之間隔件(θ=2.2°)或圖9(b)中顯示之比較實施例2中之間隔件 (θ=2.9°)朝閒置空間傾斜地更多。經測得間隔件之傾斜角為大約6.5度。將此增效效應概述如下：2.9°(外部)+2.2°(內部)→6.5°(總計)
實施例2
以與實施例1實質上相似的方式製備模板及沉積SiO膜，除了轉換內層及外層。換言之，將SiO膜沉積為SiO雙層圖案轉移膜，其係由以與比較實施例2實質上相似之方式沉積之具有20nm厚度之內部SiO單層膜(SiO(n=3))、及以與比較實施例1實質上相似之方式沉積之具有15nm厚度之外部SiO單層膜(SiO(n=0))所構成。該SiO雙層圖案轉移膜具有95%之仿形性。圖9中之(e)顯示SiO雙層膜之橫截面圖的STEM照片。換言之，具有20nm厚度之內層係具有-169.3MPa之應力的SiO單層膜(相對地壓縮性)，而具有15nm厚度之外層係具有-10.7MPa之應力的SiO單層膜(相對地拉伸性)。
接下來，使SiO雙層膜及SiARC膜在與比較實施例1中相同的條件下進行回蝕製程，隨後在與比較實施例1中相同的條件下進行灰化製程，從而形成間隔件。圖9中之(f)顯示由SiO雙層膜製成之間隔件之橫截面圖的STEM照片。如圖9中之(f)中顯示，間隔件經由核心移除(即灰化製程)相較於圖9(a)中顯示之比較實施例1中之間隔件(θ=2.2°)或圖9(b)中顯示之比較實施例2中之間隔件(θ=2.9°)朝閒置空間傾斜地更少。經測得間隔件之傾斜角為大約0.8度。將此相反效應概述如下：2.2°(外部)+2.9°(內部)→0.8°(總計)
如以上於實施例1及2中所述，經由操控內層及外層之膜應力，可形成具有期望傾斜角的間隔件。
實施例3
以與實施例1實質上相似的方式製備模板及沉積SiO膜，除了內層 係以與針對參考實施例1中於表8中之SiO(n=2)者實質上相似的方式沉積，來替代實施例1中之SiO(n=3)。
接下來，使用該雙層膜作為圖案轉移膜及在與比較實施例1中相同的條件下進行回蝕製程，隨後在與比較實施例1中相同的條件下進行灰化製程，從而形成間隔件。獲得由雙層圖案轉移膜製成之間隔件之橫截面圖的STEM照片，且測量各實施例之間隔件的傾斜角。圖10係顯示在傾斜角與雙層圖案轉移膜之外層與內層間之膜應力差異之間的關係圖。
實施例4及5
在實施例4中，製備模板，以與針對參考實施例1中於表8中之SiN(RF=3.3s)者實質上相似的方式沉積厚度20nm之SiN膜作為雙層膜的內層，且以與針對參考實施例1中於表8中之SiO(n=0)者實質上相似的方式沉積厚度15nm之SiO膜作為雙層膜的外層。所得之雙層圖案轉移膜具有100%之仿形性。
在實施例5中，製備模板且以與實施例4實質上相似的方式沉積雙層膜(仿形性為90%)，除了SiN厚度為25nm及SiO厚度為10nm。
接下來，使用於實施例4及5中獲得之各雙層膜作為圖案轉移膜及在與比較實施例1中相同的條件下進行回蝕製程來蝕刻外部SiO層，除了實施例4之施加RF功率的持續時間為14秒及實施例5為10秒，直至內部SiN層的表面幾乎暴露出來為止。其後如下表11中所示改變用來蝕刻內部SiN層的蝕刻條件。
Figure 107140247-A0202-12-0037-11
其後在表9中顯示的條件下進行SiARC層之蝕刻製程，除了施加RF功率的持續時間為9秒。其後在與比較實施例1相同的條件下進行灰化製程，從而形成間隔件。獲得由各雙層圖案轉移膜製成之間隔件之橫截面圖的STEM照片，且測量各實施例之間隔件的傾斜角。圖10係顯示在傾斜角與各雙層圖案轉移膜之外層與內層間之膜應力差異之間的關係圖。
比較實施例3
製備模板及以與比較實施例1(n=0)實質上相似的方式沉積SiO單層圖案轉移膜，除了n為2。
接下來，使用該單層膜作為圖案轉移膜及在與比較實施例1中相同的條件下進行回蝕製程，隨後在與比較實施例1中相同的條件下進行灰化製程，從而形成間隔件。獲得由單層圖案轉移膜製成之間隔件之橫截面圖的STEM照片，且測量間隔件的傾斜角。圖10係顯示單層圖案轉移膜(「比較例3」)之傾斜角的圖，其中推測膜之內半部與外半部之間的差異為零。
比較實施例4
製備模板及以與參考實施例1中針對SiN者實質上相似的方式 (RF=3.3s)沉積SiN單層圖案轉移膜。
接下來，使用該單層膜作為圖案轉移膜及在與比較實施例1中相同的條件下進行回蝕製程，隨後在與比較實施例1中相同的條件下進行灰化製程，從而形成間隔件。獲得由單層圖案轉移膜製成之間隔件之橫截面圖的STEM照片，且測量間隔件的傾斜角。圖10係顯示單層圖案轉移膜(「比較例4」)之傾斜角的圖，其中推測膜之內半部與外半部之間的差異為零。
如圖10所示(其亦描繪實施例1及2及比較實施例1及2之結果)，於負方向中之膜應力差異愈大，間隔件的傾斜角就變得於正方向中愈大(向內傾斜)，而於正方向中之膜應力差異愈大，間隔件的傾斜角就變得於負方向中愈大(向外傾斜)。因此，經由操控內層及外層的膜應力，可形成具有期望傾斜角(例如，±2°或±1°之範圍)的間隔件。
實施例6
製備模板及以與實施例4實質上相似的方式形成SiN/SiO雙層膜。所得之雙層膜具有100%之仿形性。
接下來，以與實施例4實質上相似的方式使用該雙層膜作為圖案轉移膜及進行回蝕製程，隨後進行灰化製程，從而形成間隔件。在表11中顯示的蝕刻條件下，SiO層的乾式蝕刻速率為0.4nm/秒，而SiN層的乾式蝕刻速率為1.5nm/秒。圖11顯示用來顯示「肩部損失」(圈起部分)之橫截面圖的STEM照片，其中(a)顯示於比較實施例1中形成之間隔件，及(b)顯示於實施例6中形成之間隔件。肩部損失可基於間隔件104之傾斜斜率的高度H1來評估，其在圖11之(a)中為40nm，而間隔件108(由內部SiN層108a及外部SiO層108b構成)之傾斜斜率的高度H2為5nm。如圖11所示，經由使用於內層與外層之間具有乾式蝕刻速率差異的雙層圖案轉移膜，間隔件的頂部變得實質上平坦。平坦化機制的理論據認為係稍早說明於圖12中者。
實施例7
在此實施例中，證實圖12中說明的平坦化機制。圖13顯示橫截面圖的STEM照片，其在步驟(a)至(f)中顯示自雙層膜形成具有平坦頂部之間隔件的步驟。在(a)中，製備模板且以與實施例5實質上相似的方式形成SiN/SiO雙層膜。在(b)中，蝕刻外部SiO層且內部SiN層即將暴露出來。於內部SiN層幾近暴露出來之後(例如，於(b)後不久)，蝕刻條件自針對SiO之條件(表9)轉變為針對SiN之條件(表11)。當藉由離子轟擊進行乾式蝕刻時，外層及內層之頂部部分於(c)中移除，且歸因於內層與外層間之乾式蝕刻速率(DER)的差異(在該等蝕刻條件下內層的DER高於外層的DER)，外層的頂部如(c)中之圓圈所示成為尖頭。離子於內層的經暴露表面上反射並轟擊外層的尖頭部分，藉此移除外層的尖端並使外層的頂部平坦化，如(d)中之圓圈所示，同時蝕刻內層的經暴露表面。在(d)中，內層的頂部亦經平坦化。此可能係由於歸因於在沉積內層時電漿轟擊的累積，因而內層的內部部分較內層的外部部分更嚴重受損(內部部分較外部部分暴露至電漿更長時間)。其後，進行灰化製程以移除核心材料101，如(e)中所示。所得間隔件的最終輪廓示於(f)。在此實施例中，間隔件的傾斜角為1.5度。如前所述，經由操控內層與外層間之乾式蝕刻速率的差異，可使間隔件的頂部變得實質上平坦，此外，經由操控內層及外層之膜應力，可形成具有期望傾斜角的間隔件。此等間隔件高度有用且有利於SDDP或SADP，及任何其他半導體製造過程。
熟悉技藝人士當明瞭可進行許多及各種修改而不脫離本發明之精神。因此，應清楚明瞭本發明之形式僅為說明性而非意欲限制本發明之範疇。
1‧‧‧基板
2‧‧‧電極
3‧‧‧反應室
4‧‧‧電極
5‧‧‧轉移室
6‧‧‧排氣管線
7‧‧‧排氣管線
11‧‧‧反應區
12‧‧‧電接地
13‧‧‧圓管
14‧‧‧分隔板
16‧‧‧轉移區
20‧‧‧HRF功率
21‧‧‧氣體管線
22‧‧‧氣體管線
23‧‧‧氣體管線
24‧‧‧氣體管線

Claims (16)

  1. 一種形成用於間隔件界定圖案化之間隔件的方法，其步驟包括(i)將圖案轉移膜沉積於具有藉由形成於下伏層上之心軸圖案化之表面的模板上，(ii)乾式蝕刻其整個上表面覆蓋有圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之圖案轉移膜的頂部部分及形成於下伏層上之圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下形成於心軸側壁上之圖案轉移膜的側壁部分作為間隔件，及(iii)乾式蝕刻該核心材料，從而形成閒置空間，藉此該模板具有藉由下伏層上之間隔件圖案化的表面，該等間隔件以第一傾斜角朝閒置空間向內傾斜，該第一傾斜角係定義為參考垂直於閒置空間底部之線所測得之各側壁部分之內面的角度，其中傾斜角為零代表完全垂直及傾斜角為正值代表向內傾斜，其中改良處包括：在步驟(i)中，沉積在深度方向中具有不同膜應力之仿形圖案轉移膜作為圖案轉移膜，其中該仿形圖案轉移膜之下半部具有第一膜應力及該仿形圖案轉移膜之上半部具有第二膜應力，其中該第一膜應力較該第二膜應力更具壓縮性，藉此在步驟(iii)中，該等間隔件以小於該第一傾斜角之第二傾斜角朝該閒置空間向內傾斜，其中：該仿形圖案轉移膜係由第一層及沉積於該第一層上之第二層構成，其中該第一層之膜應力較該第二層之膜應力更具壓縮性，且該第一層之厚度為該第一及該第二層之總厚度的25%至75%，該第一層具有較該第二層低的抗乾式蝕刻性，及該第一層與該第二層間之抗乾式蝕刻性的差異係使得在步驟(ii)中，各間隔件之頂部藉由抑制間隔件因乾式蝕刻引起的肩部損失而變得實質上平坦。
  2. 如請求項1之方法，其中該第二傾斜角係在大約-1°至大約1°之範圍內。
  3. 如請求項1之方法，其中該等多個層係藉由電漿增強型原子層沉積(PEALD)來沉積。
  4. 如請求項1之方法，其中該第一層之膜應力與該第二層之膜應力之間的差異係介於大約150MPa與大約800MPa之間。
  5. 如請求項1之方法，其中該等第一及第二層係獨立地由氧化矽或氮化矽構成。
  6. 如請求項5之方法，其中該第一層係由氮化矽構成及該第二層係氧化矽。
  7. 如請求項5之方法，其中該等第一及第二層係由氧化矽構成。
  8. 如請求項1之方法，其中該等第一及第二層係由不同組成物構成。
  9. 一種形成用於間隔件界定圖案化之間隔件的方法，其步驟包括(i)將圖案轉移膜沉積於具有藉由形成於下伏層上之心軸圖案化之表面的模板上，(ii)乾式蝕刻其整個上表面覆蓋有圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之圖案轉移膜的頂部部分及形成於下伏層上之圖案轉移膜的水平部分，同時留下心軸作為核心材料及留下形成於心軸側壁上之圖案轉移膜的側壁部分作為間隔件，及(iii)乾式蝕刻該核心材料，從而形成閒置空間，藉此該模板具有藉由下伏層上之間隔件圖案化的表面，該等間隔件以第一傾斜角朝該閒置空間向內傾斜，該第一傾斜角係定義為參考垂直於閒置空間底部之線所測得之各側壁部分之內面的角度，其中傾斜角為零代表完全垂直及傾斜角為正值代表向內傾斜，其中改良處包括：在步驟(i)中，沉積在深度方向中具有不同膜應力之仿形圖案轉移膜作為圖 案轉移膜，其中該仿形圖案轉移膜之下半部具有第一膜應力及該仿形圖案轉移膜之上半部具有第二膜應力，其中該第一膜應力較該第二膜應力更具壓縮性，藉此在步驟(iii)中，該等間隔件以小於該第一傾斜角之第二傾斜角朝該閒置空間向內傾斜，其中該仿形圖案轉移膜具有在深度方向中改變的膜應力，其中該膜應力係在向外方向中逐漸地增加。
  10. 如請求項9之方法，其中該仿形圖案轉移膜係由多個層構成。
  11. 如請求項10之方法，其中該等多個層係由第一層及沉積於該第一層上之第二層構成，其中該第一層之膜應力較該第二層之膜應力更具壓縮性，且該第一層之厚度為該第一及該第二層之總厚度的25%至75%。
  12. 如請求項10之方法，其中該等多個層係由第一層及沉積於該第一層上之第二層構成，其中該第一層之膜應力較該第二層之膜應力更具壓縮性，且該第一層之厚度係等於或大於該第二層之厚度。
  13. 如請求項11之方法，其中該第一層具有較該第二層低的抗乾式蝕刻性。
  14. 一種形成用於間隔件界定多重圖案化之垂直間隔件的方法，其包括：(i)在反應空間中提供具有藉由形成於下伏層上之心軸圖案化之表面的模板；(ii)沉積具有第一膜應力之第一仿形圖案轉移膜，及將具有第二膜應力之第二仿形圖案轉移膜連續地沉積於該模板的整個圖案化表面上，其中該第一及該第二膜應力不同；(iii)乾式蝕刻其整個上表面覆蓋有該第一及該第二圖案轉移膜的該模板，及藉此選擇性地移除形成於心軸頂部上之該第一及該第二圖案轉移膜的一部分及 該第一及該第二圖案轉移膜的水平部分，同時留下該心軸作為核心材料及留下該第一及該第二圖案轉移膜的垂直部分作為垂直間隔件；及(iv)乾式蝕刻該核心材料，從而在該等垂直間隔件之間形成閒置空間，藉此該模板具有藉由下伏層上之該等垂直間隔件圖案化的表面，該方法進一步包含：(v)測量該垂直間隔件的傾斜角，其係定義為參考垂直於閒置空間底部之線所測得之面向該閒置空間之該垂直間隔件之內面的角度，其中傾斜角為零代表完全垂直及傾斜角為正值代表向內傾斜，隨後判定該傾斜角是否在目標範圍內；(vi)再次進行步驟(i)至(iv)：(a)如該傾斜角在預設範圍內，則不進行改變來形成最終垂直間隔件；(b)如該傾斜角大於預設範圍，則進行改變，其中沉積具有較該第一膜應力高出一可測量程度之壓縮應力的仿形圖案轉移膜來作為步驟(ii)中之該第一仿形圖案轉移膜，及/或沉積具有較該第二膜應力高出一可測量程度之拉伸應力的仿形圖案轉移膜來作為步驟(ii)中之該第二仿形圖案轉移膜；或(c)如該傾斜角小於預設範圍，則進行改變，其中沉積具有較該第一膜應力低至一可測量程度之壓縮應力的仿形圖案轉移膜來作為步驟(ii)中之該第一仿形圖案轉移膜，及/或沉積具有較該第二膜應力低至一可測量程度之拉伸應力的仿形圖案轉移膜來作為步驟(ii)中之該第二仿形圖案轉移膜；及(vii)若進行步驟(vi)中之(b)或(c)，則於增加(b)或(c)中所使用之該可測量程度後，重複步驟(v)及(vi)，其中該第一仿形圖案轉移膜具有第一抗乾式蝕刻性，及該第二仿形圖案轉移膜具有第二抗乾式蝕刻性；及步驟(v)進一步包括判定該垂直間隔件之頂部是否實質上平坦，其中若該垂直間隔件之頂部並非實質上平坦，則：在步驟(vi)中，沉積具有較該第一抗乾式蝕刻性以及較該第二仿形圖案轉移 膜低至一可測量程度之抗乾式蝕刻性的第一仿形圖案轉移膜來作為該第一仿形圖案轉移膜，及/或沉積具有較該第二抗乾式蝕刻性以及較該第一仿形圖案轉移膜高出一可測量程度之抗乾式蝕刻性的第二仿形圖案轉移膜來作為該第二仿形圖案轉移膜；及在步驟(vii)中，於增加該可測量程度後重複步驟(v)及(vi)，直至該垂直間隔件之頂部實質上平坦為止。
  15. 一種形成用於間隔件界定圖案化之間隔件的方法，其步驟包括(i)將圖案轉移膜沉積於具有藉由形成於下伏層上之心軸圖案化之表面的模板上，(ii)乾式蝕刻其整個上表面覆蓋有圖案轉移膜的模板，及藉此選擇性地移除形成於心軸頂部上之圖案轉移膜的頂部部分及形成於下伏層上之圖案轉移膜的水平部分，同時留下該心軸作為核心材料及留下形成於該心軸側壁上之該圖案轉移膜的側壁部分作為間隔件，及(iii)乾式蝕刻該核心材料，從而形成閒置空間，藉此該模板具有藉由下伏層上之間隔件圖案化的表面，其中面向該閒置空間之各間隔件的肩部部分(該肩部部分係該間隔件頂部的外部轉角)被移除或蝕刻，從而形成自該間隔件頂部之外側至內側的傾斜表面，其中改良處包括：在步驟(i)中，沉積由包括第一層及沉積於該第一層上之第二層之雙層膜構成的仿形圖案轉移膜作為該圖案轉移膜，其中該第一層具有較該第二層低的抗乾式蝕刻性，其中該第一層與該第二層間之抗乾式蝕刻性的差異係使得在步驟(iii)中，各間隔件之頂部藉由抑制該間隔件因乾式蝕刻引起的肩部損失而變得實質上平坦。
  16. 如請求項15之方法，其中該第一層係由氮化矽構成，及該第二層係由氧化矽構成。
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