TWI834919B - 氧化矽之拓撲選擇性膜形成之方法 - Google Patents

氧化矽之拓撲選擇性膜形成之方法 Download PDF

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TWI834919B
TWI834919B TW109134744A TW109134744A TWI834919B TW I834919 B TWI834919 B TW I834919B TW 109134744 A TW109134744 A TW 109134744A TW 109134744 A TW109134744 A TW 109134744A TW I834919 B TWI834919 B TW I834919B
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film
silicon nitride
nitride film
silicon oxide
oxide film
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TW109134744A
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TW202129053A (zh
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深澤篤毅
財津優
陳珮嘉
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荷蘭商Ａｓｍ Ｉｐ私人控股有限公司
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    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract

一種在形成於基板上之步階上形成氧化矽膜之方法，包括：(a)設計最終氧化矽膜之拓撲，其係經由參照起始氮化矽膜之非目標部分預選擇待選擇性地沉積或移除或重整藉以產生最終氧化矽膜之起始氮化矽膜之目標部分；及(b)根據於製程(a)中設計之拓撲於步階之表面上形成起始氮化矽膜及最終氧化矽膜，其中起始氮化矽膜係經由ALD使用含有鹵素之含矽前驅物來沉積，及經由氧化起始氮化矽膜來將起始氮化矽膜轉變為最終氧化矽膜而不進一步沉積膜，其中將起始氮化矽膜中之Si-N鍵轉變為Si-O鍵。

Description

氧化矽之拓撲選擇性膜形成之方法
本發明大致上係關於一種在形成於基板上之步階上形成氧化矽膜之方法，該步階具有頂表面、側壁、及底表面，特定而言，係關於一種氧化矽之拓撲選擇性膜形成之方法。
原子層沉積(ALD)方法包括電漿增強型原子層沉積(PEALD)方法被廣泛地使用於半導體製造過程中作為一種於具有一圖案化表面之基板上形成一共形膜的方法。在一些半導體製造過程中，使一經形成為共形膜的膜經受乾蝕刻或其他乾式修整製程以各向異性地移除膜的一或多個部分供特定應用之用。在該情況中，膜形成製程及蝕刻製程需於兩個分開的步驟中進行。
然而，當使薄膜經受蝕刻時，例如，薄膜、下層膜、及遮罩材料的蝕刻選擇性(即，薄膜、下層膜、及遮罩材料之間之耐蝕刻性的差異程度)始終是一個議題，且對下層膜的不良影響(例如，下層膜之品質因穿透離子能量而退化，及溝槽之臨界尺寸(CD)的退化)係無可避免的。
如膜形成本身可藉由各向異性沉積及/或各向異性重整製程控制膜之拓撲，則無需乾蝕刻或其他乾式修整製程來消除乾蝕刻對下層膜的不良影響，藉以降低製程步驟的數目，及增加產出量。然而，由於在膜沉積製程中氧化係相當各向同性地發生，因而控制氧化矽膜的拓撲係相當困難的。
關於此類控制膜之拓撲的技術，已知首先在某些條件下將SiN膜沉積在基板的圖案化表面上，使得圖案之水平部分及垂直部分的濕蝕刻速率不同，隨後進行濕蝕刻，藉以選擇性地僅留下圖案的側壁部分或圖案的水平部分(例如，如美國專利公開案第2017/0243734號中所揭示，其揭露之全文係以引用方式併入本文中，如適用於本文所揭示的某些實施例)。該技術可稱為SiN之拓撲選擇性膜形成(「TS-SiN」)。在上文中，由於使用濕蝕刻而非乾蝕刻來選擇性地僅移除圖案的垂直部分或水平部分，可行的係設定圖案相對於下層膜的高濕蝕刻選擇性，並實現不需要考慮蝕刻均勻性的優點。在TS-SiN中，高濕蝕刻選擇性可藉由增加RF功率來得到；然而，此類條件無法在SiO膜上運作以達成類似的高濕蝕刻選擇性。因此，雖然在半導體產業中對於SiO之拓撲選擇性膜形成(「TS-SiO」)存在高度需求，卻並未成功地實現TS-SiO。
關於相關技術之問題及解決方案的任何論述，僅出於提供本發明之背景脈絡的目的而包括於本揭露中，且不應被視為承認任何或全部該論述在進行本發明時為已知。
在一些實施例中，經由首先將SiN膜選擇性地沉積於沉積在基板之步階中之SiO膜的水平表面上來將拓撲選擇性SiO(TS-SiO)膜形成於基板之步階中，其中水平表面(步階之頂表面及底表面)主要經由使SiO膜暴露至具有相當高離子能量之含NH3-或N2/H2-電漿藉由各向異性電漿選擇性地處理(此表面處理可稱為「培養」或「表面氮化」)，隨後主要選擇性地於步階之水平表面上使用含鹵素之前驅物進行SiN膜的PEALD(此沉積製程可稱為「氮化」)，其中吸附於基板表面上之前驅物經氮化，其中前驅物中之鹵素藉由交換反應(例如，Si-Cl→Si-N)經氮化氣體中之氮置換，藉以形成 SiN之一單層。作為一第二製程，所沉積的SiN膜經由氧化處理轉變為SiO膜(此處理可稱為「氧化」)，以致所得膜之主要組分為SiO，且由於各向異性氮化可於膜一經轉變為SiO膜後重複，因此所得膜可僅於或主要地於垂直方向中生長，藉此可達成各向異性PEALD。
各向異性氮化或選擇性氮化係藉由各向異性或選擇性培養或表面氮化達成，其之各向異性現象係歸因於含氮電漿的各向異性離子入射。為處理SiO表面，需要超過特定水平的離子能量，及因此，可實質上僅於或主要地於暴露至離子能量之SiO膜的一部分處達成各向異性表面處理，藉以於表面上導入-NH端。另一方面，當氧化SiN膜時，氧化可容易地藉由電漿發生而不用離子能量輔助，即可均勻地於圖案化結構上完成氧化處理。
當圖案化結構包括具有高縱橫比及狹窄開口之溝槽時，注射至溝槽內部中的離子數目小於輻射於頂表面上的離子數目。因此，與頂表面相比，不會於溝槽內部發生氮化。經由利用以上現象，當圖案具有狹窄開口時，可選擇性地及主要地僅於頂表面上形成SiO膜。適用於以上操作之縱橫比及開口尺寸的可工作範圍係視諸如沉積壓力及RF功率的沉積條件而異。
各向異性或選擇性培養或表面氮化在SiN膜沉積於其上之下層SiO膜的表面上形成-NH端。關於用來沉積SiN膜之前驅物，可使用任何能夠吸附於具有經暴露之Si-NH表面之下層SiO膜上，但幾乎不會吸附於Si-O表面上之前驅物，諸如SiCl4、Si2Cl6、及其類似物。
於視需要藉由氧化處理將SiN膜轉變為SiO膜後，可使用(例如)dHF使圖案化結構經受濕蝕刻，以致可移除任何作為殘留物殘留於側壁上之SiO膜，藉以形成完成的TS-SiO膜。儘管原則上，SiN膜僅沉積於頂表面上，但用來沉積SiN膜之前驅物的表面選擇性，即選擇性地於Si-NH表面上，而非於Si-O表面上之沉積可能並不完全。在該情況，SiN膜可輕微地 沉積於側壁上，由於氧化係各向同性地發生，因而其經轉變為SiO膜。經由使圖案化結構經受濕蝕刻，可移除側壁上之殘留SiO膜。應注意不管位置為何，SiO膜的濕蝕刻速率大約為2.2(參照熱氧化物膜的濕蝕刻速率為1)，即SiO膜之頂部部分、SiO膜之側壁部分、及SiO膜之底部部分的濕蝕刻速率實質上或大致相等。因此，儘管濕蝕刻不僅蝕刻SiO膜之側壁部分並且亦蝕刻頂部部分，但由於SiO膜之頂部部分主要或實質地較其之側壁部分厚，因而可獲得完成的TS-SiO膜。
在一些實施例中，用來沉積SiN膜之前驅物不含碳，且最終氧化矽膜不含碳，藉此可避免包括自SiN膜遷移之碳之雜質分散至SiN膜與下層膜之間的界面中。於將SiN膜轉變為SiO膜後，可形成亦不含碳的SiO膜。經由形成不含碳的SiO膜，可避免下層膜的品質因經由SiO膜與下層膜間之界面進入下層膜之諸如碳之雜質(其係遷移自SiO膜)所引起的任何退化。
一些實施例之特徵在於使用含有鹵素之不含碳之無機前驅物以及不含碳之反應物。照慣例，當使用含有鹵素之前驅物時，沉積係在含氮烴(直鏈或環狀)反應物(諸如吡啶)的輔助下進行，其中氮通過交換反應(例如，Cl
Figure 109134744-A0305-02-0006-8
N)置換吸附於基板上之前驅物中之鍵結至矽的鹵素(例如，Cl-Si)，藉以形成由SiN材料構成的膜。然而，由於反應化合物包含烴，因而一些碳殘留於膜中的可能性係不可忽視的。此外，在一些情況中，前驅物包含烴。經由使用含有鹵素之不含碳之無機前驅物及不含碳之反應物，可藉由PEALD沉積不含碳之SiN膜，隨後進行轉變製程，其中經由氧化處理將SiN膜轉變為SiO膜。
當重複以上製程以形成具有期望厚度的SiO膜時，如在沉積SiN膜的過程之前(即在饋送前驅物之前)，不含碳之前驅物於SiO表面上 的吸附不足，將導致每循環的生長(GPC)降低及/或步階覆蓋率降低，則可使SiO表面暴露至NH3、N2/H2、及其類似物之電漿，以改良前驅物於基板表面上之吸附。
拓撲選擇性處理技術不限於前述實施例。拓撲選擇性處理技術係一種基本上組合藉由PEALD使用含有鹵素之含矽前驅物形成氮化物膜，及將氮化物膜氧化的技術，且在一些實施例中包括以下三種技術： 1)藉由ALD或CVD於圖案化基板上沉積SiO薄膜，然後藉由PEALD使用含鹵素前驅物經由操控或調整RF功率來沉積SiN膜，其中歸因於各向異性培養或表面氮化製程(其中水平面較垂直面接受到更多離子能量且表面氮化實質上僅於或主要於水平面、而非於垂直面上發生)，SiN膜選擇性地生長於圖案化基板的水平面，特定而言頂面上； 2)藉由ALD(熱或電漿增強型)使用含鹵素之前驅物於圖案化基板上沉積SiN膜，然後使用氧化材料諸如O2在電漿能量、UV光能量、熱能、或其他能量之輔助下將SiN膜轉變為SiO膜，隨後進行濕蝕刻，其中SiN膜係經由施加100至1,000W之RF功率持續5秒或以下來沉積，以致沉積於側壁上之膜之一部分的氮化變得不完全，且該部分對濕蝕刻的阻力變得不足，藉以經由濕蝕刻移除側壁上之膜的該部分及留下沉積於水平面上之膜的一部分；及 3)於以上2)中，當沉積SiN膜時經由施加100至1,000W之RF功率超過5秒，諸如對濕蝕刻之阻力的膜性質在沉積於頂面上之膜之一部分、沉積於側壁上之膜之一部分、及沉積於底面上之膜之一部分之間可實質上相等，藉此，於濕蝕刻後，可形成共形SiO膜(不含碳)。在本揭露中，雖然針對300-mm基板來指示RF功率，但當將RF功率用於具有不同直徑之基板時，可針對基板經由計算每基板面積之瓦數(W/cm2)來確定適用的RF 功率。
在一些實施例中，前驅物係選自不含碳、含鹵素之矽烷基化合物，及反應物(氮化氣體)係選自N2/H2、NH3、或其他NxHy(x及y不為零)中之至少一者。
在一些實施例中，不含碳、含鹵素之矽烷基化合物包括，但不限於，二碘矽烷、二氯矽烷、六氯二矽烷、及八氯三矽烷，其可單獨地或以前述兩者或更多者之任何組合使用。
在一些實施例中，氮化(經由交換反應用氮置換鹵素)及氧化係於相同反應室中依序連續地進行，其中於氮化後，使用惰性氣體沖洗反應室，然後將氧化氣體諸如O2、O3、CO2、N2O、H2O、及其類似物或前述兩者或更多者之組合饋送至腔室及進行氧化，藉以形成SiO膜。
在一些實施例中，氮化及氧化不須經重複相同次數，但經由調整及改變氮化及氧化的重複次數及調整RF功率，可降低膜對濕蝕刻的阻力(例如，經由增加氧化的重複次數、降低用於氮化的RF功率、及/或提高用於氧化的RF功率)。
在一些實施例中，經由調整形成於頂面、側壁、及底面上之膜對濕蝕刻的阻力(濕蝕刻速率)，頂面、側壁、及底面的各別部分可選擇性地經移除或維持通過濕蝕刻(例如，使用dHF)。
在一些實施例中，當經由PEALD進行氮化及氧化時，有時，前驅物於基板表面上的吸附程度於氧化後降低，在該情況中，經由於氧化後使用含氫之還原氣體諸如H2、NH3、或其類似物改良基板之表面狀況，可改良含鹵素前驅物的吸附性質，藉以提高每循環之生長(GPC)。
在本揭露中，除非另外說明，否則SiN、SiO、SiOC、或其類似者係以非化學計量方式指示膜類型的簡寫。
為了概述本發明之態樣及所達成之優於相關技術之優點的目的，在本揭露中描述本發明之某些目標及優點。當然，應瞭解的是，可無須根據本發明之任何特定實施例來達成所有此類目標或優點。因此，例如，所屬技術領域中具有通常知識者將認知到，可以達成或最佳化如本文中所教示之一個優點或一組優點而無須達成本文中可教示或建議之其他目標或優點的方式來體現或實行本發明。
本發明之進一步的態樣、特徵及優點，將由下文的詳細描述而變得顯而易見。
1:基板
2:導電平板電極
3:反應室
4:導電平板電極
5:轉移室
6:排氣管線
7:排氣管線
11:反應室之內部(反應區)
12:電接地之一側
13:圓管
14:分隔板
16:轉移室的內部(轉移區)
20:HRF功率
21:氣體管線
22:氣體管線
23:氣體管線
24:密封氣體管線
30:瓶(儲槽)
41:基板
42:步階
43:SiO膜
44:SiNH表面
46:SiN膜
51:基板
52:步階
53:SiN膜
54:SiO膜
61:基板
62:步階
63:SiN膜
64:SiO膜
a:閥
b:閥
c:閥
d:閥
e:閥
f:閥
現將參照意欲說明而非限制本發明之較佳實施例的圖式來描述本發明的這些及其他特徵。圖式係經大幅度簡化以供說明性目的使用，且未必按比例繪製。
圖1A係可用於本發明之一實施例中之用於沉積保護膜之PEALD(電漿增強型原子層沉積)設備的示意圖。
圖1B繪示可用於本發明之一實施例中之使用流通系統(FPS)之前驅物供應系統的示意圖。
圖2係根據本發明之一實施例繪示拓撲選擇性膜形成製程的流程圖。
圖3係根據本發明之另一實施例繪示拓撲選擇性膜形成製程的流程圖。
圖4係根據本發明之又另一實施例繪示拓撲選擇性膜形成製程的流程圖。
圖5係根據本發明之又另一實施例繪示拓撲選擇性膜形成製程的流程圖。
圖6係繪示根據本發明之一實施例之拓撲選擇性膜形成製程之序列的時間圖，其中各欄的寬度不一定代表實際的時間長度，且各列中線的高 起水平代表開-狀態，而各列中線的底部水平代表關-狀態。
圖7係繪示根據本發明之另一實施例之拓撲選擇性膜形成製程序列的圖表，其中灰色格子表示「開」狀態，而白色格子表示「關」狀態，且各欄之寬度不代表各製程的持續時間。
圖8係顯示習知膜形成製程之序列的圖表，其中灰色格子表示「開」狀態，而白色格子表示「關」狀態，且各欄之寬度不代表各製程的持續時間。
圖9繪示顯示根據本發明之一實施例之拓撲選擇性膜形成製程的示意橫截面圖。
圖10繪示顯示根據本發明之另一實施例之拓撲選擇性膜形成製程的示意橫截面圖。
圖11繪示顯示根據本發明之又另一實施例之拓撲選擇性膜形成製程的示意橫截面圖。
在本揭露中，「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。在本揭露中，透過噴淋頭導入至反應室之製程氣體可包含前驅物氣體及添加劑氣體、基本上由前驅物氣體及添加劑氣體組成、或由前驅物氣體及添加劑氣體組成。前驅物氣體及添加劑氣體一般係作為混合氣體或分開地導入至反應空間。前驅物氣體可使用載體氣體(諸如稀有氣體)導入。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分開地導入至反應空間。前驅物可包含二或更多種前驅物，且反應物氣體可包含二或更多種反應物氣體。前驅物係化學吸附於基板上且一般含有構成介 電膜基質之主結構的類金屬或金屬元素的氣體，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物起反應的氣體。「化學吸附」係指化學飽和吸附，其亦可簡稱為「吸附」。可使用除製程氣體外之氣體(即，非通過噴淋頭導入之氣體)以用於例如密封反應空間，該氣體包括諸如稀有氣體之密封氣體。在一些實施例中，「膜(film)」係指用以覆蓋整個目標或關注表面，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，覆蓋目標或關注表面之層。在一些實施例中，「層(layer)」係指形成於表面上之具有特定厚度之結構或者膜或非膜結構之同義詞。膜或層可由具有某些特性之離散單一膜或層或者由多個膜或層構成，且相鄰膜或層之間的邊界可明確或可不明確，並可基於物理、化學、及/或任何其他特性、形成製程或序列、及/或相鄰膜或層之功能或用途而建立。
在本揭露中，「含有Si-O鍵」可指特徵在於一或多個Si-O鍵，其具有實質上由一或多個Si-O鍵構成的主骨架及/或具有實質上由一或多個Si-O鍵構成的取代基。含有Si-O鍵的介電膜包括，但不限於SiO膜、SiOC膜、及SiON膜，其具有約2至10、一般約4至8之介電常數。
進一步地，在本揭露中，除非另外指明，否則冠詞「一(a或an)」係指一個物種或包括多個物種之屬。在一些實施例中，用語「由......構成(constituted by)」及「具有(having)」係獨立地指「一般或廣泛地包含(typically or broadly comprising)」、「包含(comprising)」、「基本上由......組成(consisting essentially of)」或「由......組成(consisting of)」。同樣地，在本揭露中，在一些實施例中，任何已定義之意義未必排除常規及慣用意義。
此外，在本揭露中，變數之任何兩個數目可構成變數之可工作範圍，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。此外，所指示的變數之任何數值(不管該等數值是否以「約」來指示)可指精確值或近似值並包括等效值，且在一些實施例中可指平均值、中間值、代表值、多數值等。
在本揭露中條件及/或結構未得到具體規定之處，熟悉本技藝者可鑒於本揭露輕易提供此類條件及/或結構，作為例行實驗主題。在所有已揭示實施例中，於一實施例中所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，本發明可同等地適用於設備及方法。
將參考較佳實施例來解釋該等實施例。然而，本發明並未受限於該等較佳實施例。
一例示性實施例係關於一種基於PEALD技術的介電膜形成製程，其中使用電漿藉由各向異性表面處理實質上僅對或主要對圖案化模板的水平面進行表面處理，然後使膜選擇性地生長於經表面處理面上。膜生長主要發生於垂直方向上同時抑制在水平方向中的膜生長，藉此獲得具有期望拓撲的膜輪廓。藉由此技術，在基板的頂面及基板之凹部的側壁之間，膜可實質上僅沉積於基板之頂面上。術語「實質上僅」係指，例如，總量的70%、80%、90%、或95%或更高，例如，沉積於頂面上之膜之一部分的平均厚度對沉積於側壁上之膜之一部分的平均厚度的比係7/3或更高。
於底面上之膜形成程度係取決於縱橫比，例如，儘管底面亦係水平面。如溝槽的縱橫比高，例如，3或更高(當開口尺寸為50nm或以下時)，與在暴露至離子轟擊之頂面上之離子量相比，進入溝槽之離子量變低。結果，表面氮化或藉由表面處理之培養(SiO表面之氮化處理)在底面上的進行程度不如在頂面上般高，因此，生長於底面上之膜的厚度小於生長於頂面上之膜的厚度。經由調整凹部之縱橫比，例如，使用具有10或更高之縱橫 比的凹部，可在頂面、側壁、及底面之間，實質上地將膜沉積於頂面上。
在一些實施例中，拓撲選擇性製程包含：A)使用電漿以實質上僅處理圖案化基板之水平面的方式進行各向異性表面處理(培養或表面氮化)；B)經由PEALD使用含有鹵素活性基之前驅物及NH3、N2/H2、及其類似物之電漿於經表面處理面上沉積氮化物膜(經由鹵素與氮間之交換反應的氮化)；C)經由於沖洗腔室之後饋受(例如)O2來將反應室中之氣體改變為氧化氛圍，及經由(例如)熱氧化、自由基氧化、電漿氧化等等將氮化物膜氧化，以將氮化物膜轉變為氧化物膜；及D)重複步驟A)至C)直至氧化物膜之厚度達到期望值，其中氧化物膜具有期望的拓撲選擇性膜輪廓。
在一些實施例中，氧化物膜係由SiO、SiOC、SiON、及其類似物構成。由於進行各向異性表面處理，因此膜實質上僅於垂直方向中，而非於水平方向中生長。經由使用具高縱橫比之凹部，在頂面、側壁、及底面之間，膜可實質上僅形成於頂面上。此外，視需要，經由使最終經沉積之氧化物膜經受各向同性濕蝕刻(例如，使用dHF)，可完全移除側壁上之膜，藉以形成其中僅頂面及底面上之膜可殘留的膜輪廓。此外，在一些實施例中，表面處理及沉積製程可使用相同反應室連續地進行。
在拓撲選擇性處理技術中，經由使用不含碳之前驅物及不含碳之氮化反應物諸如N2、N2/H2、NH3、或其類似物沉積SiN膜，然後經由使用諸如O2、H2O、或其類似物之氧化氣體通過氧化交換反應氧化SiN膜將SiN膜轉變為SiO膜，可達成形成生長於基板上之不含碳之SiO膜。藉由此技術，可在進行SiO膜形成時抑制製程氣體(包括前驅物及反應物)中所含之雜質累積於SiO膜與下層膜之間的界面中。
一些實施例提供一種在形成於基板上之具有頂表面、側壁、及底表面之步階上形成氧化矽膜之方法，其包括以下製程：(a)設計最終氧化 矽膜之拓撲，最終氧化矽膜為共形膜或具低共形性之膜，最終氧化矽膜係經由參照起始氮化矽膜之非目標部分預選擇待選擇性地沉積或移除或重整藉以產生最終氧化矽膜之起始氮化矽膜之目標部分而形成於步階上，該經選擇性沉積之目標部分係形成於步階之頂表面及底表面上之起始氮化矽膜的頂部/底部部分，該經選擇性移除或重整之目標部分係形成於步階側壁上之起始氮化矽膜的側壁部分；及(b)根據於製程(a)中設計之拓撲於步階之表面上形成起始氮化矽膜及最終氧化矽膜，其中起始氮化矽膜係經由原子層沉積(ALD)使用含有鹵素之含矽前驅物來沉積，及經由氧化起始氮化矽膜來將起始氮化矽膜轉變為最終氧化矽膜而不進一步沉積膜，其中將起始氮化矽膜中之Si-N鍵轉變為Si-O鍵。圖2係代表拓撲選擇性膜形成之以上製程的流程圖。如圖2中所說明，存在三種替代地或以任何組合使用以達成最終氧化物膜之期望拓撲的技術：選擇性沉積膜的目標部分、選擇性移除膜的目標部分、及選擇性重整膜的目標部分。
在本揭露中，用語「步階(step)」或「凹部(recess)」係指形成在基板中之由相對參考平面(底面)之上升部(側壁)及階面(頂面)構成的任何圖案化結構，且在一些實施例中，步階可係一溝槽，其具有約10至約50nm(一般約15至約30nm)之寬度(其中當溝槽具有與寬度實質上相同的長度時，其係稱為孔/通孔，且其直徑係約10至約50nm)，深度係約30至約200nm(一般約50至約150nm)，及縱橫比約3至約20(一般約3至約10)。在一些實施例中，最終氧化矽膜係選擇性地形成於頂面上(具有約零至約10%、約20%、或約30%或以下的共形性)或沿基板之步階或溝槽均勻地形成(具有約70%至約110%、一般約80%或更高、更一般約90%或更高、及100%或以下的共形性)，其中「共形性(conformality)」係藉由比較形成在凹部之側壁或底面上之某一點(一般係橫截面圖的中間點)處之膜厚度相對 形成於正好凹部外側之平坦表面(頂面)上之膜厚度來判定。
在一些實施例中，於製程(b)中使用之前驅物不含碳，且最終氧化矽膜不含碳。
在一些實施例中，起始氮化矽膜之形成(其可稱為「氮化」，其中反應物之氮經由交換反應置換經吸附前驅物之鹵素)及起始氮化矽膜之氧化係於製程(b)中於相同反應空間中連續地進行。在一些實施例中，於形成起始氮化矽膜之後於氧化起始氮化矽膜之前沖洗反應空間，及起始氮化矽膜之氧化係於經導入氧化氣體(其係選自由O2、O3、CO2、N2O、及H2O組成之群的至少一種氣體)之反應空間中進行的電漿氧化。在本揭露中，於一些實施例中，「連續地」係指不中斷真空、在時間線上無中斷、未改變處理條件、其後立即、作為下一步驟、或在兩結構間無離散的物理或化學邊界。氮化一般需實質上地完成，因為氮化物膜中之任何殘留鹵素可被視為雜質(如同碳)，其會遷移至氮化物膜與下層膜之間的界面中。
在一些實施例中，起始氮化矽膜係由多個單層構成，及在製程(b)中，起始氮化矽膜之氧化係於起始氮化矽膜之ALD的各次單層沉積循環之後或於起始氮化矽膜之ALD的每次多個單層沉積循環之後進行。
在一些實施例中，於製程(a)中預選擇的目標部分係經選擇性沉積的目標部分，其中製程(b)包含：(ci)將氧化矽膜沉積於基板上之步階的表面上；(cii)使用經由於兩電極(基板平行於兩電極置於其間)之間施加RF功率所產生之含氮氫電漿以主要於步階之頂表面及底表面上，而非於步階之側壁上氮化氧化矽膜之表面的方式各向異性地氮化氧化矽膜之表面，從而導入氧化矽膜之表面上的-NH端；(ciii)經由ALD使用前驅物及經由在兩電極之間施加RF功率所產生之電漿來激發的氮化氣體在經表面處理之氧化矽膜上且與其接觸地沉積至少部分的起始氮化矽膜；(civ)使用經激發的氧化氣體來氧 化至少部分的起始氮化矽膜以得到至少部分的最終氧化矽膜而不進一步沉積膜，其中起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵；及(cv)視需要，重複製程(cii)至(civ)直至獲得具有期望厚度的最終氧化矽膜。圖3係代表拓撲選擇性膜形成之以上製程的流程圖。
在一些實施例中，製程(cii)中之含氮氫電漿係使用N2及H2之混合物、NH3、其他NxHy(其中x及y係整數)、或前述中兩者或兩者以上的混合物來產生。
在一些實施例中，製程(ci)中之氧化矽膜係藉由ALD或CVD來沉積。
在一些實施例中，於製程(a)中預選擇的目標部分係經選擇性移除的目標部分，其中製程(b)包括：(di)經由ALD使用前驅物及經由在兩電極(基板平行於兩電極置於其間)之間施加RF功率所產生之電漿來激發的反應物氣體將至少部分的起始氮化矽膜沉積於基板上之步階之表面上，其中在ALD之各次單層沉積循環中RF功率係以每基板面積0.14W/cm2至1.41W/cm2施加5秒或以下，從而得到當經受濕蝕刻時耐化學性性質較非目標部分低之目標部分；(dii)使用經激發的氧化氣體來氧化至少部分的起始氮化矽膜以得到至少部分的中間氧化矽膜而不進一步沉積膜，其中起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵；及(diii)視需要，重複製程(di)及(dii)直至獲得具有期望厚度的中間氧化矽膜；然後(div)濕蝕刻中間氧化矽膜以得到最終介電膜，藉此參照非目標部分主要地移除目標部分。圖4係代表拓撲選擇性膜形成之以上製程的流程圖。
在一些實施例中，製程(dii)中之氧化係使用電漿、UV光、熱、或前述中兩者或兩者以上的組合來實施。
在一些實施例中，製程(di)中使用之RF功率係每基板面積 0.14W/cm2至0.71W/cm2，及製程(dii)中之氧化係於製程(di)中於起始氮化矽膜之ALD的各次單層沉積循環之後或於起始氮化矽膜之ALD的每次多個單層沉積循環之後進行的電漿氧化，其中電漿係經由在兩電極(基板平行於兩電極置於其間)之間以每基板面積0.07W/cm2至0.71W/cm2施加RF功率來產生。
在一些實施例中，進行製程(diii)，其中緊接在每次重複製程(di)之前，使基板之步階之表面暴露至含氫還原氣體，以利用含氫還原氣體處理表面。
在一些實施例中，含氫還原氣體係選自由H2及NH3所組成之群之至少一種氣體。
在一些實施例中，於製程(div)中，濕蝕刻係使用dHF之濕蝕刻。
在一些實施例中，於製程(a)中預選擇的目標部分係經選擇性重整的目標部分，其中製程(b)包括：(ei)經由ALD使用前驅物及經由在兩電極(基板平行於兩電極置於其間)之間施加RF功率所產生之電漿來激發的反應物氣體將至少部分的起始氮化矽膜沉積於基板上之步階之表面上，其中在ALD之各次單層沉積循環中RF功率係以每基板面積0.14W/cm2至1.41W/cm2施加超過5秒，從而得到當經受濕蝕刻時耐化學性性質實質上與非目標部分相等之目標部分；(eii)使用經激發的氧化氣體來氧化至少部分的起始氮化矽膜以得到至少部分的中間氧化矽膜而不進一步沉積膜，其中起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵；及(eiii)視需要，重複製程(ei)及(eii)直至獲得具有期望厚度的中間氧化矽膜；然後(eiv)濕蝕刻中間氧化矽膜以得到最終介電膜，藉此形成具高共形性的最終氧化矽膜。圖5係代表拓撲選擇性膜形成之以上製程的流程圖。
在一些實施例中，製程(eii)中之氧化係使用電漿、UV光、熱、或前述中兩者或兩者以上的組合來實施。
在一些實施例中，製程(ei)中使用之RF功率係每基板面積0.71W/cm2至1.41W/cm2，及製程(eii)中之氧化係於製程(ei)中於起始氮化矽膜之ALD的各次單層沉積循環之後或於起始氮化矽膜之ALD的每次多個單層沉積循環之後實施的電漿氧化，其中電漿係經由在兩電極(基板平行於兩電極置於其間)之間以每基板面積0.07W/cm2至0.71W/cm2施加RF功率來產生。
在一些實施例中，進行製程(eiii)，其中緊接在每次重複製程(ei)之前，使基板之步階之表面暴露至含氫還原氣體，以利用含氫還原氣體處理表面。
在一些實施例中，含氫還原氣體係選自由H2及NH3所組成之群之至少一種氣體。
在一些實施例中，於製程(eiv)中，濕蝕刻係使用dHF之濕蝕刻。
在一些實施例中，蝕刻係使用dHF之濕蝕刻，其濃度大約為0.1%。
將參照圖式中所繪示的較佳實施例詳細解釋本發明。然而，本發明並非意欲受到這些實施例的限制。
圖6係繪示根據本發明之一實施例之拓撲選擇性膜形成製程之序列的時間圖，其中各欄的寬度不一定代表實際的時間長度，且各列中線的高起水平代表開-狀態，而各列中線的底部水平代表關-狀態。藉由此技術，可藉由選擇性沉積膜的目標部分(頂部部分)來形成頂部厚TS-SiO膜。
在圖6中，膜之目標部分(頂部部分)的選擇性沉積包括三個製 程：培養製程、氮化(沉積)製程、及氧化製程。在培養製程之前，在圖案化基板上之步階之表面上沉積氧化矽膜作為下層膜。培養製程包括使用利用氮化氣體(反應物1)經由於兩電極(基板平行於兩電極置於其間)之間施加RF功率(處理3)所產生之含氮氫電漿以主要於步階之頂表面及底表面上，而非於步階之側壁上氮化氧化矽膜之表面的方式各向異性地氮化氧化矽膜之表面，從而於氧化矽膜之表面上導入-NH端。在培養製程中，在一些實施例中，反應物1之流動速率係在500sccm至10000sccm(較佳1000sccm至5000sccm)範圍內，及處理3係在1秒至20秒(較佳3秒至10秒)之範圍內。
接下來，開始氮化(沉積)製程，其包括經由PEALD使用前驅物(前驅物)及經由在兩電極之間施加RF功率(處理1)所產生之電漿來激發的氮化氣體(反應物1)在經表面處理之氧化矽膜上且與其接觸地沉積至少部分的起始氮化矽膜。培養製程中之處理3及氮化製程中之處理1皆係經由施加RF功率的處理。儘管在處理3及處理1兩者中RF功率施加的條件可相同。然而，在一些實施例中，較佳地，處理3使用較處理1強的離子能量以進行各向異性表面氮化。因此，在一些實施例中，在處理3中，使用較處理1中高的RF功率及/或低的壓力。舉例來說，在處理3中，在100Pa至3000Pa(較佳200Pa至1000Pa)之壓力下施加在0.07W/cm2至1.4W/cm2(較佳0.14W/cm2至0.7W/cm2)範圍內之RF功率，而在處理1中，在100Pa至2000Pa(較佳200Pa至1000Pa)之壓力下施加在0.07W/cm2至1.4W/cm2(較佳0.14W/cm2至0.7W/cm2)範圍內之RF功率。氮化(沉積)製程係PEALD製程，可將其用於形成一單層的一個循環重複N次，直到得到氮化物膜的所欲厚度，其中取決於膜的預期用途等，N係10至1000的整數(較佳地係10至30)，以便沉積具有5nm至100nm(較佳地10nm至30nm)厚度之氮化物膜。在PEALD之一個循環中，前驅物、反應物1、及處理1之脈衝的持 續時間係在0.1秒至20秒之範圍內。
其後，開始氧化製程，其包括使用經由RF功率(處理2)激發的氧化氣體(反應物2)來氧化至少部分的起始氮化矽膜，以得到至少部分的最終氧化矽膜而不進一步沉積膜，其中起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵。舉例來說，在處理2中，在100Pa至3000Pa(較佳200Pa至1000Pa)之壓力下施加在0.07W/cm2至1.4W/cm2(較佳0.07W/cm2至0.7W/cm2)範圍內之RF功率。在氧化製程中，在一些實施例中，反應物2之流動速率係在10sccm至1000sccm(較佳50sccm至500sccm)之範圍內，及處理2之持續時間係在0.1秒至20秒(較佳0.5秒至10秒)之範圍內。
在整個製程中，將在500sccm至10000sccm(較佳1000sccm至5000sccm)範圍內之惰性氣體(惰性氣體)連續地饋送至反應室。並且，製程溫度可在0℃至600℃(較佳地200℃至500℃)的範圍內。
此外，視需要，可將培養製程、氮化製程、及氧化製程重複M次，直到得到具有期望厚度之最終氧化矽膜，其中取決於膜的預期用途等，M係1至30的整數(較佳地係1至15)。
圖9繪示顯示根據由圖6中繪示之時間圖所表示之一實施例之拓撲選擇性膜形成製程的示意橫截面圖。狀態(a)表示於狀態(b)前之狀態，其中將SiO膜43形成於具有步階42(溝槽)之基板41之表面上。狀態(b)表示於培養製程後之狀態，其中經由各向異性含氮電漿氮化SiO膜43之表面，以致於SiO表面上導入-NH端，從而於SiO膜43上形成SiNH表面44。狀態(c)表示於氮化製程後之狀態，其中SiN膜46經由PEALD沉積且生長於SiNH表面44上。當使SiN膜46經受氧化製程時，SiN膜46經轉變為類似於狀態(a)中之SiN膜43的SiN膜。然後，重複此等製程，從而於基板上獲得期望的最終SiO膜(頂部厚TS-SiO膜)。
在一些實施例中，選擇性沉積流程可在下表1中所示的條件下實施。
Figure 109134744-A0305-02-0021-1
圖7係繪示根據本發明之另一實施例之拓撲選擇性膜形成製程序列的圖表，其中灰色格子表示「開」狀態，而白色格子表示「關」狀態，且各欄之寬度不代表各製程的持續時間。藉由此技術，頂部厚TS-SiO膜可藉由選擇性移除膜之目標部分(側壁)來形成，此外，共形TS-SiO膜可藉由選擇性重整膜之目標部分(相對於側壁之頂面)來形成。
此製程序列包括氮化/沉積製程(「饋送」→「沖洗」→「RF脈衝-1(氮化/還原)」→「沖洗」)、氧化製程(「反應物-2進」→「RF脈衝-2(氧化)」→「沖洗」)、及濕蝕刻製程(「DHF浸漬」)。氮化製程包括經由PEALD使用前驅物(Si前驅物)及經由於兩電極(基板平行於兩電極置於其間)之間施加RF功率(RF)所產生之電漿來激發的反應物氣體(反應物-1)於基板上之步階之表面上沉積至少部分的起始氮化矽膜，其中在PEALD之各次單層沉積循環中RF功率係以每基板面積0.14W/cm2至1.41W/cm2(較佳地0.07W/cm2至0.71W/cm2)施加5秒或以下(較佳1秒至3秒)，從而得到當經受濕蝕刻時耐化學性性質(對濕蝕刻之阻力)較非目標部分低的目標部分(側壁)。經由使用以上的RF功率施加條件，沉積於側壁上之膜的一部分未經充分氮化，而與沉積於頂面/底面上之膜的一部分相比保持對濕蝕刻的阻力，從而容 許經由濕蝕刻選擇性地移除側壁部分。
氮化(沉積)製程係PEALD製程，可將其用於形成一單層的一個循環重複q次直到得到所欲厚度的氮化物膜，其中取決於膜的預期用途等，q係10至1000的整數(較佳地係30至500)，以便沉積具有5nm至100nm(較佳地10nm至30nm)厚度之氮化物膜。在PEALD之一個循環中，「Si-前驅物」、「反應物-1」、及「RF」之脈衝的持續時間係在0.1秒至20秒(較佳地0.1秒至10秒)之範圍內。在一些實施例中，RF功率係在100Pa至2000Pa(較佳地200Pa至1000Pa)之壓力下施加。在氮化製程中，在一些實施例中，反應物-1之流動速率係在500sccm至10000sccm(較佳地2000sccm至5000sccm)之範圍內。在此實施例中，「反應物-1」及「載體氣體/稀釋氣體」連續地流動。
接下來，開始氧化製程，其包括使用經由RF功率(RF)激發的氧化氣體(反應物-2)來氧化至少部分的起始氮化矽膜，以得到至少部分的中間氧化矽膜而不進一步沉積膜，其中起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵。舉例來說，在100Pa至2000Pa(較佳200Pa至1000Pa)之壓力下施加在0.07W/cm2至1.4W/cm2(較佳0.07W/cm2至0.7W/cm2)範圍內之RF功率。在氧化製程中，在一些實施例中，「反應物-2」之流動速率係在10sccm至1000sccm(較佳50sccm至500sccm)之範圍內，及「RF」之持續時間係在0.1秒至10秒(較佳0.1秒至5秒)之範圍內。
在整個製程中，可將在500sccm至10000sccm(較佳1000sccm至5000sccm)範圍內之載體氣體及/或稀釋氣體連續地饋送至反應室。並且，製程溫度可在0℃至600℃(較佳地200℃至500℃)的範圍內。
此外，視需要，將氮化/沉積製程及氧化製程重複p次，直到得到具有期望厚度之中間氧化矽膜，其中取決於膜的預期用途等，p係1至 30的整數(較佳地係1至15)。
其後，開始濕蝕刻製程(DHF浸漬)，其包括濕蝕刻中間氧化矽膜以得到最終介電膜，藉此參照非目標部分主要地移除目標部分(側壁)。在一些實施例中，濕蝕刻可經由使用氫氟酸或其之以0.1%至1.5%稀釋之已知或新的適宜等效物/替代物在15℃至25℃之溫度下蝕刻基板持續30秒至600秒來進行。
圖10繪示顯示根據由圖7中繪示之製程序列表示之一實施例之拓撲選擇性膜形成製程的示意橫截面圖。狀態(a)表示於氮化/沉積製程後之狀態，其中將SiN膜53形成於具有步階52(溝槽)之基板51之表面上。狀態(b)表示於氧化製程後之狀態，其中使SiN膜53經受氧化製程，及將SiN膜53轉變為SiO膜54。其後，視需要，重複氮化/沉積製程及氧化製程，直到得到所欲厚度的SiO膜。狀態(c)表示於濕蝕刻後之狀態，其中經由濕蝕刻，由於沉積於側壁上之膜部分具有較頂面/底面部分低的耐濕蝕刻性，因此膜的側壁部分可選擇性地經顯著移除或選擇性地經完全移除，同時其他部分可維持顯著厚度。因此，可於基板上形成期望的最終SiO膜(頂部厚TS-SiO膜)。
經由使用繪示於圖7中之相同製程，除了在ALD之各次單層沉積循環中於兩電極間施加的RF功率為每基板面積0.14W/cm2至1.41W/cm2(較佳地0.07W/cm2至0.71W/cm2)持續超過5秒之外，所得SiO膜之膜性質諸如耐濕蝕刻性可在沉積於頂面上之膜部分、沉積於側壁上之膜部分、及沉積於底面上之膜部分之間變得實質上相等，藉此，於濕蝕刻後，可形成共形SiO膜(不含碳)。
圖11繪示顯示由圖7中繪示之製程序列(其係如以上論述經修改)表示之拓撲選擇性膜形成製程的示意橫截面圖。狀態(a)表示於氮化/沉 積製程後之狀態，其中將SiN膜63形成於具有步階62(溝槽)之基板61之表面上。狀態(b)表示於氧化製程後之狀態，其中使SiN膜63經受氧化製程，及將SiN膜63轉變為SiO膜64。其後，視需要，重複氮化/沉積製程及氧化製程，直到得到所欲厚度的SiO膜。狀態(c)表示於濕蝕刻後之狀態，其中經由濕蝕刻，由於沉積於頂面上之膜部分、沉積於側壁上之膜部分、及沉積於底面上之膜部分具有實質上相似的耐濕蝕刻性，因此所有部分視需要實質上相等地經蝕刻。因此，可於基板上形成期望的最終SiO膜(共形不含碳、均質TS-SiO膜)。
在一些實施例中，在選擇性移除目標部分(圖10)及選擇性重整目標部分(圖11)中之氮化可在下表2中顯示的條件下進行。
Figure 109134744-A0305-02-0024-2
在一些實施例中，在選擇性重整流程中，為改良膜的共形性，含氮氣體的流動速率較於選擇性移除流程中者大，此外，RF功率施加時間較於選擇性移除流程中者長。換言之，在一些實施例中，在選擇性移除流程中，為相對於在垂直表面上增加膜在平坦(水平)表面上之生長，含氮氣體的流動速率較於選擇性重整流程中者低，此外，RF功率施加時間較於選擇性重整流程中者短。
圖8係顯示習知膜形成製程之序列的圖表，其中灰色格子表示「開」狀態，而白色格子表示「關」狀態，且各欄之寬度不代表各製程的 持續時間。由於在習知製程中，未進行對應於或等效於彼等以上針對本發明之實施例所論述的製程，因此邏輯上，將不會形成共形不含碳、均質的SiO膜。
在本揭露中所述之製程序列中，前驅物可使用連續供應之載體氣體以脈衝供應。此可使用流通系統(FPS)來完成，其中載體氣體管線具備具有前驅物儲槽(瓶)之歧路管線，且主管線及歧路管線經切換，其中當僅意欲將載體氣體饋送至反應室時，關閉歧路管線，而當意欲將載體氣體及前驅物氣體兩者饋送至反應室時，主管線關閉且載體氣體流過歧路管線且與前驅物氣體一起從瓶流出。以此方式，載體氣體可連續地流入反應室中，且可藉由切換主要管線及歧路管線而以脈衝載送前驅物氣體。圖1B繪示根據本發明之一實施例之使用流通系統(FPS)的前驅物供應系統(黑色閥指示該等閥關閉)。如圖1B中之(a)所示，當將前驅物饋送至反應室(未圖示)時，首先，諸如Ar(或He)之載體氣體流過具有閥b及c之氣體管線，且接著進入瓶(儲槽)30。載體氣體從瓶30流出，同時載送對應於瓶30內之蒸氣壓的量之前驅物氣體，並流過具有閥f及e之氣體管線，且接著與前驅物一起饋送至反應室。在上文中，閥a及d關閉。當僅將載體氣體(稀有氣體)饋送至反應室時，如圖1B中之(b)所示，載體氣體流過具有閥a之氣體管線，同時繞過瓶30。在上文中，閥b、c、d、e、及f關閉。
前驅物可借助載體氣體來提供。由於ALD係自限制吸附反應製程，因此所沉積之前驅物分子的數目係藉由反應性表面位點之數目來判定，且與飽和後之前驅物暴露無關，且前驅物之供應係使得反應性表面位點因而在每一循環均飽和。用於沉積之電漿可原位(例如，在整個沉積循環中連續流動的氨氣中)產生。在其他實施例中，電漿可於遠端產生並提供至反應室。
如上文所提及，各沉積循環之各脈衝或階段較佳係自限制的。在各階段中供應過量的反應物以使敏感的結構表面飽和。表面飽和確保反應物佔據所有可用的反應性位點(遭受例如實體大小或「位阻(steric hindrance)」限制)，且因此確保優越的步階覆蓋。在一些實施例中，可減少反應物之一或多者的脈衝時間，使得完全飽和未達成，且小於一單層經吸附在基板表面上。
例如，可使用包括圖1A所繪示之設備的任何合適設備來執行製程循環。圖1A係可用於本發明之一些實施例中之PEALD設備(所欲的係與經程式化以實施下述序列之控制機構協力)的示意圖。在此圖式中，藉由在反應室3之內部11(反應區)中提供平行且彼此面對的一對導電平板電極4、2，向一側施加HRF功率(13.56MHz或27MHz)20，且將另一側12電氣接地，在該等電極之間激發電漿。溫度調節器係在下部台2(下部電極)中提供，且放置在其上之基板1的溫度在給定溫度下保持恆定。上部電極4亦充當噴淋板，且反應物氣體(及稀有氣體)及前驅物氣體分別透過氣體管線21及氣體管線22以及透過噴淋板4導入反應室3中。此外，在反應室3中，提供具有排氣管線7之圓管13，透過該排氣管線將反應室3之內部11中的氣體排出。此外，稀釋氣體係透過氣體管線23導入反應室3中。進一步地，經設置於反應室3下方之轉移室5具備密封氣體管線24以經由轉移室5之內部16(轉移區)將密封氣體導入反應室3之內部11中，其中提供用於將反應區與轉移區分開之分隔板14(此圖省略閘閥，晶圓經由該閘閥轉移至轉移室5中或從該轉移室轉移)。轉移室亦具有排氣管線6。在一些具體例中，多元素膜沉積及表面處理在同一反應空間中執行，以使得所有步驟可連續進行，而不會將基板暴露於空氣或其他含氧氛圍中。在一些具體例中，遠端電漿單元可用於激發氣體。
在一些實施例中，於圖1A所描繪之設備中，可在實質上不使反應室壓力波動的情況下使用圖1B所繪示之切換惰性氣體流及前驅物氣體流的系統(先前描述)以脈衝導入前驅物氣體。
在一些實施例中，可使用雙室反應器(經設置為彼此靠近之用於處理晶圓的兩個區段或隔室)，其中反應物氣體及稀有氣體可通過共用管線供應，而前驅物氣體係通過非共用管線供應。
所屬技術領域中具有通常知識者應瞭解，設備包括一或多個控制器(未圖示)，其(等)經程式化或以其他方式組態以導致實施本文於別處所述之沉積及反應器清潔製程。如所屬技術領域中具有通常知識者將瞭解的，(多個)控制器係與反應器之各種電源、加熱系統、泵、機器人系統、及氣流控制器或閥通訊。
本發明將參照下文之工作例以進一步解釋。然而，實例並非意欲限制本發明。在未指定條件及/或結構之實例中，所屬技術領域中具有通常知識者可鑒於本揭露而按照例行實驗輕易地提供此類條件及/或結構。同樣地，在一些實施例中，特定實例中所應用之數字可在至少±50%之範圍內進行修改，且該等數字為近似值。
實例
實例1
在此實例中，進行如圖5中所說明之膜之目標部分的選擇性重整。首先，經由PEALD於具有溝槽(具有30nm之開口及3之縱橫比)之Si基板(Φ300mm)上形成具有20nm厚度之SiN膜，然後，使用繪示於圖1A中之PEALD設備及繪示於圖1B中之氣體供應系統(FPS)，根據圖7中繪示之製程序列在表3中顯示的一般條件及下表4中顯示之特定條件下將SiN膜轉變為SiO膜。其後，使基板在下文表3中顯示的條件下經受濕蝕刻。作 為比較實例，根據圖8中繪示之製程序列以類似於上述之方式沉積SiO膜，其中不進行氮化/沉積製程且不進行氧化(轉變)製程。
Figure 109134744-A0305-02-0028-3
Figure 109134744-A0305-02-0028-5
評估各SiO膜，及結果示於下表5。
Figure 109134744-A0305-02-0028-6
Figure 109134744-A0305-02-0029-7
表5中，「根據沖洗時間的GPC趨勢」中之「飽和」指示根據GPC(每循環之生長)，沖洗過程係以於PEALD之各循環中之反應過程係於經吸附前驅物之飽和下進行的方式進行；「側面覆蓋率」係指共形性(%)；「PLE」係指窄維度與寬維度之比；「100：1 DHF-WERR(TOX比)」係指使用以1%稀釋之氫氟酸之相對於熱氧化物膜的濕蝕刻速率；於「碳」中「<5」係指偵測得碳小於5原子%；及「ND」係指「未偵測」。
如表5所示，根據實例，於所有實例中獲得的SiO膜係高品質的共形不含碳SiO膜，而於比較實例中，SiO膜係較低品質的SiOC膜。
熟習此項技術者應理解，可進行許多及各種修改而不背離本發明之精神。因此，應清楚理解，本發明之形式僅係說明性，而非意欲限制本發明之範疇。

Claims (12)

  1. 一種在形成於基板上之具有頂表面、側壁、及底表面之步階上形成氧化矽膜之方法，其包括以下製程：(a)設計一最終氧化矽膜之一拓撲，該最終氧化矽膜為一共形膜或一具低共形性之膜，該最終氧化矽膜係經由參照一起始氮化矽膜之一非目標部分預選擇待選擇性地沉積或移除或重整藉以產生該最終氧化矽膜的一起始氮化矽膜之一目標部分地形成於該步階上，經選擇性沉積之該目標部分係形成於該步階之該頂表面及該底表面上之該起始氮化矽膜的一頂部/底部部分，經選擇性移除或重整之該目標部分係形成於該步階的該側壁上之該起始氮化矽膜的一側壁部分；及(b)根據於製程(a)中設計之該拓撲於該步階之表面上形成該起始氮化矽膜及該最終氧化矽膜，其中該起始氮化矽膜係經由一原子層沉積(ALD)使用含有鹵素之一含矽前驅物來沉積，及經由氧化該起始氮化矽膜來將該起始氮化矽膜轉變為該最終氧化矽膜而不進一步沉積膜，其中該起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵，其中於製程(a)中預選擇的該目標部分係經選擇性沉積的該目標部分，其中製程(b)包括：(ci)將氧化矽膜沉積於該基板上之該步階的表面上；及(cii)使用經由於兩電極之間施加RF功率所產生之含氮氫電漿主要對該步階之該頂表面及該底表面上的該氧化矽膜之表面，而不對該步階之該側壁上的該氧化矽膜之表面進行氮化的方式，各向異性地氮化該氧化矽膜之表面，藉以於該氧化矽膜之表面上導入-NH端，其中該基板平行於該兩電極地設置於該兩電極間。
  2. 如請求項1所述之方法，其中於製程(b)中使用之該前驅物不含碳，且該最終氧化矽膜不含碳。
  3. 如請求項1所述之方法，其中該起始氮化矽膜之形成及該起始氮化矽膜之氧化係於製程(b)中於相同的一反應空間中連續地進行。
  4. 如請求項3所述之方法，其中於形成該起始氮化矽膜之後且氧化該起始氮化矽膜之前沖洗該反應空間，及該起始氮化矽膜之氧化係於經導入氧化氣體之該反應空間中進行的電漿氧化，該氧化氣體係選自由O2、O3、CO2、N2O、及H2O組成之群的至少一種氣體。
  5. 如請求項1所述之方法，其中該起始氮化矽膜係由多個單層構成，及在製程(b)中，該起始氮化矽膜之氧化係於該起始氮化矽膜之ALD的各次單層沉積循環之後或於該起始氮化矽膜之ALD的每次多個單層沉積循環之後進行。
  6. 如請求項1所述之方法，其中製程(b)更包括：(ciii)經由ALD使用該前驅物及經由在該兩電極之間施加RF功率所產生之電漿激發的氮化氣體在經表面處理之該氧化矽膜上且與其接觸地沉積至少部分的該起始氮化矽膜；(civ)使用經激發的氧化氣體來氧化至少部分的該起始氮化矽膜以得到至少部分的該最終氧化矽膜而不進一步沉積膜，其中該起始氮化矽膜中之Si-N鍵經轉變為Si-O鍵；及(cv)視需要，重複製程(cii)至(civ)直至獲得具有期望厚度的該最終氧化矽膜。
  7. 如請求項6所述之方法，其中製程(cii)中之該含氮氫電漿係使用N2及H2之混合物、NH3、其他NxHy，其中x及y係整數、或前述中兩者或兩者以上的混合物來產生。
  8. 如請求項6所述之方法，其中製程(ci)中之該氧化矽膜係藉由ALD或CVD來沉積。
  9. 如請求項1所述之方法，其中含有鹵素之該含矽前驅物包括SiCl4以及Si2Cl6中的一者或多者。
  10. 如請求項1所述之方法，更包括一濕蝕刻步驟。
  11. 如請求項1所述之方法，其中各向異性地氮化該氧化矽膜的步驟包括提供選自N2/H2、NH3、或其他NxHy(x及y不為零)氣體中之至少一者的一氮化氣體。
  12. 如請求項1所述之方法，其中含有鹵素之該含矽前驅物包括二碘矽烷、二氯矽烷、六氯二矽烷、及八氯三矽烷中之一或多者，且為單獨地或任何組合。
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