TW201437416A - 低收縮介電薄膜 - Google Patents

低收縮介電薄膜 Download PDF

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TW201437416A
TW201437416A TW102148000A TW102148000A TW201437416A TW 201437416 A TW201437416 A TW 201437416A TW 102148000 A TW102148000 A TW 102148000A TW 102148000 A TW102148000 A TW 102148000A TW 201437416 A TW201437416 A TW 201437416A
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ruthenium
plasma
containing precursor
substrate processing
substrate
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Suk-Won Hong
Toan Tran
Abhijit Mallick
Jing-Mei Liang
Nitin K Ingle
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Applied Materials Inc
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Abstract

本發明描述在基板上形成介電層之方法，且該方法可包括將第一前驅物引入至遠端電漿區域中，該遠端電漿區域與基板處理腔室之基板處理區域流體耦接。可在遠端電漿區域中形成電漿以產生電漿流出物。可將電漿流出物導入至基板處理區域中。可將含矽前驅物引入至基板處理區域中，且含矽前驅物可包括至少一個矽-矽鍵。可在處理區域中使電漿流出物及含矽前驅物反應以形成矽基介電層，該介電層在基板上形成時起初為可流動的。

Description

低收縮介電薄膜 【相關專利申請案之交叉引用】
本申請案主張於2013年3月15日提交申請之美國非臨時專利申請案第13/834,333號之優先權，該美國非臨時專利申請案主張於2013年1月25日提交申請之標題為「Low Shrinkage Dielectric Films」之美國臨時申請案第61/756,762號之權益。出於所有目的以全文引用之方式將以上每個揭示案併入本文。
本發明技術係關於半導體製程及設備。更特定而言，本發明技術係關於形成介電材料。
隨著積體電路晶片製造商不斷增加每個晶片上電路元件之密度，填充分離彼等元件之間隙變得更具挑戰性。增加的電路元件密度已使得相鄰元件之間更短的寬度成為必需。由於該等間隙之寬度收縮比該等間隙之高度收縮更快，故高度與寬度之比率(稱為深寬比)按比例增加。使用介電材料之均勻薄膜填充高且窄的間隙(亦即，高深寬比間隙)比填充淺且寬的間隙(亦即，低深寬比間隙)更加困難。
填充高深寬比間隙通常遭遇的一個難題係空隙之形成。在高深寬比間隙中，填充間隙之介電材料傾向於以更快的速率在間隙之頂端周圍沉積。通常，在已完全填充間隙前，介電材料將封閉頂部，留下空隙。即使當間隙之頂部並未過早閉合，介電薄膜沿間隙之側壁向下的不均勻生長速率可在間隙填充之中間產生薄弱的接縫。該等接縫稍後可導致裂痕，不利地影響裝置之實體完整性及介電特性。
一種避免介電間隙填充中形成空隙及薄弱接縫之技術係以較低沉積速率填充間隙。較低沉積速率可給予介電材料更多時間以在間隙之內表面上再分佈以減少過度頂側生長之幾率。較低沉積速率亦可係增加與介電沉積同時發生之蝕刻或濺鍍之結果。舉例而言，在HDPCVD中，間隙之頂部角落處的介電材料比間隙之側壁及底部部分上的材料蝕刻更快。此增加了間隙之頂側將保持開口之幾率，從而使得側壁及底部可完全填滿介電材料。然而，減小介電沉積速率亦導致沉積花費更長時間完成。更長的沉積時間減小了基板晶圓經由沉積腔室處理的速率，導致腔室效率下降。
因此，需要改良的系統及方法以用無空隙介電薄膜填充短寬度、高深寬比之間隙。藉由本發明之系統及方法解決該等及其他問題。
本發明描述在基板上形成介電層之方法，且該方法可包括將第一前驅物引入至遠端電漿區域中，該遠端電漿區域與基板處理腔室之基板處理區域流體耦接。可在遠端電漿 區域中形成電漿以產生電漿流出物。可將電漿流出物導入至基板處理區域中。可將含矽前驅物引入至基板處理區域中，且含矽前驅物可包括至少一個矽-矽鍵。可在處理區域中使電漿流出物及含矽前驅物反應以形成矽基介電層，該介電層在基板上形成時起初為可流動的。
含矽前驅物可包括至少兩個矽-矽鍵，且可包括三個或更多個矽-矽鍵。第一前驅物可包括選自包括氨、氮、H2、Ar及He的群組中之一或更多種前驅物，及亦可包括額外載氣或前驅物之組合。可經由淋噴頭將電漿流出物及含矽前驅物引入至處理區域中，該淋噴頭經配置以維持前驅物之分離，使得該等前驅物在進入基板處理區域前不彼此接觸。維持基板與淋噴頭相隔小於或約3吋之距離，且在所揭示之實施例中可維持基板與淋噴頭相隔更近或更遠。基板處理區域在沉積製程期間可為無電漿，及在替代配置中，可在處理區域內提供直接電漿。
含矽前驅物可具有化學式SixHy，其中x係大於或等於2，且y係2x+n或更大，其中n係小於或等於2之任何數字。亦可將含矽前驅物以實質氣相引入至處理區域中。可在小於或等於約30℃溫度下執行沉積之方法，且製程期間之壓力可為小於或等於約5托。藉由所描述之製程產生的所形成薄膜可具有大於或等於約1.4g/cc之密度。
方法亦可包括在形成矽基介電層後停止含矽前驅物之引入。然而，可將電漿流出物連續導入至基板處理區域中，以便緻密化形成的介電層。方法可進一步包括退火形成的矽 基介電層，且在退火期間，形成的矽基介電層可收縮小於約20%。
亦描述用於在處理腔室之基板處理區域中的基板上形成介電層的方法。方法可包括將第一前驅物引入至與基板處理區域流體耦接之遠端電漿區域中，同時在遠端電漿區域中形成電漿以產生電漿流出物。方法亦可包括將電漿流出物導入至基板處理區域，及將含矽前驅物引入至基板處理區域。在所揭示之實施例中，含矽前驅物可包括至少一個矽-矽鍵。方法亦可包括在基板處理區域中使電漿流出物及含矽前驅物反應以形成矽基介電層，該介電層在基板上形成時起初為可流動的。方法可進一步包括使用至少一種額外前驅物固化形成的矽基介電層。
所使用之至少一種額外前驅物可包括含氧前驅物、含氮前驅物或含碳前驅物。方法亦可包括將電漿流出物導入至基板處理區域以緻密化所固化的介電層。所使用之含矽前驅物可具有化學式SixHy，其中係x大於或等於2，且y係2x+n或更大，其中n係小於或等於2的任何數字，且其中將含矽前驅物以實質氣相引入至處理區域中。引入至處理腔室中以形成矽基介電層的前驅物可包括一或更多種惰性前驅物及具有矽-矽鍵及矽-氫鍵的含矽前驅物。方法亦可包括退火所形成的矽基介電層之步驟。當執行時，退火可將形成的介電層在退火期間收縮小於約20%。
此技術相較於習知技術可提供眾多益處。舉例而言，所揭示之沉積製程可產生更緻密且更高品質之薄膜。因 此，可在退火期間或形成後操作期間減小或防止薄膜收縮。將結合下文描述及隨附圖式更詳細地描述該等及其他實施例以及眾多優勢及特徵。
110‧‧‧操作
120‧‧‧操作
130‧‧‧操作
140‧‧‧操作
210‧‧‧操作
220‧‧‧操作
230‧‧‧操作
240‧‧‧操作
250‧‧‧操作
260‧‧‧操作
270‧‧‧操作
301‧‧‧基板處理腔室
310‧‧‧遠端電漿系統/RPS
311‧‧‧氣體入口組件
312‧‧‧第一通道
313‧‧‧第二通道
320‧‧‧腔室電漿區域
321‧‧‧蓋/導電頂部部分
324‧‧‧絕緣環
326‧‧‧長度
350‧‧‧最小直徑
351‧‧‧中空體積
353‧‧‧淋噴頭
355‧‧‧小孔
356‧‧‧通孔
370‧‧‧基板處理區域
375‧‧‧基座
380‧‧‧基板
400‧‧‧系統
402‧‧‧前端開口晶圓盒
404‧‧‧機器人臂
406‧‧‧低壓固持區域
408a‧‧‧基板處理腔室
408b‧‧‧基板處理腔室
408c‧‧‧基板處理腔室
408d‧‧‧基板處理腔室
408e‧‧‧基板處理腔室
408f‧‧‧基板處理腔室
410‧‧‧第二機器人臂
可參考本說明書之其餘部分及圖式實現對所揭示技術之本質及優勢的進一步理解。
第1圖圖示根據所揭示之實施例之用於形成介電薄膜的製程之流程圖。
第2圖圖示根據所揭示之實施例之用於形成介電薄膜的製程之另一流程圖。
第3A圖圖示根據所揭示之技術之基板處理腔室的一部分之示意性橫截面圖。
第3B圖圖示根據所揭示之技術之淋噴頭之底部平面圖。
第4圖圖示根據所揭示之技術之示例性基板處理系統之俯視平面圖。
在隨附圖式中，類似組件及/或特徵可具有相同數字元件符號。進一步，相同類型之各個組件可由元件符號後的字母區分，該字母在類似元件及/或特徵中各不相同。只要本說明書中使用第一數字元件符號，該描述便適用於具有相同第一數字元件符號的類似元件及/或特徵中之任一者而無關於字母後綴如何。
本發明技術包括用於在基板上沉積矽基材料的經改 良之製程及化學輪廓。儘管習知製程可沉積類似材料之薄膜，但是薄膜可遭受降低的品質及密度。因此，當緻密化較低品質薄膜以產生較高品質薄膜時，薄膜收縮可發生，該收縮可對底層裝置具有不良效應。舉例而言，隨著裝置幾何形狀減小，矽或裝置基座可具有更薄的壁輪廓。當在結構內部沉積薄膜及緻密化薄膜時，收縮薄膜可對底層結構施加應力，此應力可使得圖案變形。然而，本發明技術可形成基本上比習知薄膜收縮更少的可流動薄膜。在此情況下，可覆蓋更加複雜之圖案。舉例而言，裝置內部之溝槽可具有極高深寬比，諸如具有高度：寬度比率大於或約5：1、8：1、10：1等等或更高，且因此提供自下而上填充輪廓可能需要可流動介電薄膜。若緻密化時該等薄膜亦收縮更少，則對底層結構施加更少應力，及可改良總體製程品質。
本發明描述在基板上形成介電層之方法，且該等方法可包括將第一前驅物引入至遠端電漿區域中，該遠端電漿區域與基板處理腔室之基板處理區域流體耦接。可在遠端電漿區域中形成電漿以產生電漿流出物。可將電漿流出物導向至基板處理區域中。可將含矽前驅物引入至基板處理區域中，且含矽前驅物可包括至少一個矽-矽鍵。可在處理區域中反應電漿流出物及含矽前驅物以形成矽基介電層，該介電層在基板上形成時起初為可流動的。
矽基薄膜之沉積中所使用之前驅物可包括影響沉積薄膜之品質的各種額外分子。舉例而言，羥基之存在可增加沉積薄膜之流動性。然而，在最終薄膜中移除該等基團以產 生較高品質薄膜可為理想的。該等基團之移除或用包括氧、氮及碳的其他材料取代(例如)可減小沉積或形成之薄膜之總體密度。因此，當執行用於緻密化薄膜之後續處理步驟時，薄膜可收縮，此情況可產生對底層結構的不當應力。發明者已有利地決定，藉由減少所使用之前驅物中除矽以外包括的材料，所得薄膜可具有改良的品質且與基於變化更多之前驅物基團的習知薄膜相比可具有減小的收縮。
為了更好地理解及瞭解本發明，現將參考第1圖，該圖圖示根據所揭示之實施例之用於形成介電薄膜的製程之流程圖。在第一操作前，可將基板傳遞至製程腔室中，諸如下文所描述之彼等製程腔室。可預先圖案化或相對清洗基板。可能已經執行各種前端處理，包括閘極、通孔、溝槽及其他結構之形成。該等結構可為奈米尺度，且例如，需要填充的溝槽或間隙可具有小於約100nm之寬度，及或者可小於或約75nm、50nm、40nm、30nm、25nm、20nm、10nm等等或更小。可隨後將經圖案化之基板傳遞至基板處理區域以便沉積介電材料。在所揭示之實施例中，若在待發生沉積製程的同一腔室中執行先前操作，則基板可已經位於處理區域中。在操作110處，可將第一前驅物引入至處理腔室之電漿區域中，該電漿區域自基板所在腔室之處理區域分離或移除。第一前驅物可包括若干前驅物材料中之一者。舉例而言，第一前驅物可為一或更多種惰性氣體，包括氬、氦、氮等等。或者或另外，可使用額外氣體，且額外氣體可包括氨(NH3)、氫或含氮及/或含氫氣體。在所揭示之實施例中，第一前驅物 可只包括惰性氣體，及在一示例性製程中，將氬或氦傳遞至電漿區域。
分離電漿區域在本文中可稱為遠端電漿區域及可處於與處理腔室分離的不同模組內部，或稱為處理腔室內部的隔室。可在遠端電漿區域內部形成電漿，從而自第一前驅物產生電漿流出物。在操作120處，將產生的電漿流出物導入至基板處理區域中。此舉可以眾多方式實現，該等方式包括使用壓力差、產生之電場或一些其他將離子流及/或電子流導入至處理區域中之已知機制。在操作120前、操作120後或與操作120同時，可將含矽前驅物引入至基板處理區域中。在所揭示之實施例中，含矽前驅物包括至少一個矽-矽鍵。
可在基板處理區域中使電漿流出物及含矽前驅物反應以在基板上形成矽基介電層。當起初形成時或當起初沉積時，形成的材料起初可為可流動的，此情況可允許該材料向下流入至溝槽中以填充在基板上所界定之圖案。介電材料可基於電漿物質與含矽前驅物之間的反應。前驅物可在彼此接觸後直接開始反應，且因此前驅物在進入基板處理區域之前可為分離的。可藉由諸如下文將進一步描述之雙通道淋噴頭之組件執行此分離。可配置淋噴頭以維持前驅物之分離以便防止前驅物彼此接觸，直至該等前驅物進入或被傳遞至基板處理區域中。先前技術可已依賴於如此沉積的薄膜中包括水或羥基以潛在給予薄膜流動性。如先前所述，儘管如此，該等基團可產生較弱薄膜，該等薄膜在緻密化後可產生令人不可接受的收縮。然而，本發明技術使用可協同允許流動性發 生之各種參數。
不受限於特定理論，沉積薄膜中矽-矽鍵之數目可直接對應於產生薄膜之收縮量。舉例而言，薄膜中矽-矽鍵愈多，因緻密化而可發生收縮愈少，因為可給予更少額外聚合及移除不當物質更少。諸如當正在形成氧化矽薄膜時，在初始沉積後，可氧化形成的薄膜或形成的薄膜可與額外材料反應以便將氧合併至聚合物基質中，及移除諸如氫、氮、碳等等之殘餘材料。自薄膜移除的更多材料可在薄膜內部留下微孔，該等微孔在諸如退火之緻密化期間被移除。該等微孔之移除可壓縮薄膜，沿薄膜接觸之表面施加應力。該等應力可克服允許結構變形之閾值，此舉可破壞底層結構。因此，本發明技術可使用含矽前驅物，該等含矽前驅物最大化矽-矽鍵之數目及最小化額外分子鍵合。以此方式，在固化或其他操作期間可需要移除更少材料，此舉可減小最終薄膜之收縮量。
在所揭示之實施例中，該技術可使用矽烷及聚矽烷作為含矽前驅物。該等材料可包括或只由矽-矽鍵及矽-氫鍵組成。示例性前驅物可包括至少一個矽-矽鍵、至少兩個矽-矽鍵、至少三個矽-矽鍵等等。舉例而言，前驅物可選自從二矽烷開始的聚矽烷同系物中之任一者。含矽前驅物亦可選自聚矽烷之各種異構體。舉例而言，若含矽前驅物具有五個矽原子，則組合物可包括正戊矽烷、異戊矽烷、新戊矽烷、2-矽烷基四矽烷、2,2-二矽烷基三矽烷等等中之任一者。含矽前驅物可包括環狀形式或環矽烷，諸如(例如)環六矽烷。聚矽烷亦可包括任何飽和或不飽和化合物，諸如矽烯類及矽炔類。 含矽前驅物亦可具有通式，諸如SixHy。X可為2或大至無限大之任何數字，且Y可為2或大至無限大之任何數字。舉例而言，此最小式將表示二矽炔(Si2H2)。Y亦可係基於X的任何因數。舉例而言，Y可為2X或2X+N，其中n=2，0，-2，-4，-6等等，或N可為小於或等於2的任何數字。技術中所使用之示例性矽烷可包括二矽烷、四矽烷、環六矽烷等等。
該等所揭示之材料中的眾多材料之蒸氣壓係使得材料在許多操作條件下可為實質液相。儘管在所揭示之技術中可以液體形式使用含矽前驅物，但是在實施例中，可將含矽前驅物以蒸氣或實質蒸氣形式引入至處理腔室中。然而，此舉可需要使用額外元件以確保以蒸氣形式引入材料。可使用許多不同機制以傳遞氣相含矽前驅物。舉例而言，在各種其他技術中可使用有或沒有受熱安瓶、起泡器的蒸氣吸取或直接液體噴射。然而，取決於使用的前驅物，可發生額外問題。舉例而言，若將高階矽烷以液相傳遞至噴嘴，則可加熱噴嘴以將材料作為蒸氣傳遞至基板處理區域中。然而，高階矽烷之汽化溫度與高階矽烷之聚合溫度可相對接近，以使得技術可阻塞噴嘴。另外，起泡器可在蒸氣之傳遞中使用惰性氣體，並且引入額外惰性氣體。在此情況下，可需要進一步機制以確保傳遞實際含矽前驅物之適當流以提供適當薄膜形成速率。高階含矽前驅物或矽烷具有更多矽-矽鍵，此情況可導致薄膜之更少收縮，但是該等高階含矽前驅物或矽烷可另外具有極低蒸氣壓，此情況可需要額外組件或機制以提供氣相含矽前驅物至基板處理區域。
再次不受限於任何特定理論，使用所揭示之技術的介電材料之流動性可基於製程參數之組合，該等參數包括關於含矽前驅物的製程之溫度與壓力、使用的電漿功率及淋噴頭或傳遞前驅物之機制與待形成薄膜之基板之間的距離。在處理期間，基板處理區域在沉積期間可相對無電漿、實質上無電漿或完全無電漿。儘管可將第一前驅物之電漿流出物傳遞至基板處理區域中，但是在基板處理區域外部可含有用於產生流出物之電漿。在淋噴頭下或前驅物起初交互作用處可直接發生最大量之反應。電漿流出物可已具有最小量之再結合時間，且因此前驅物之間可發生更大反應。使用之材料可進一步影響該等氣相反應。矽-矽鍵可為比矽-氫、矽-氧及其他矽基鍵更弱的鍵。因此，在該等較大反應發生的情況下，或在使用較高電漿功率的情況下，對於本發明技術之含矽前驅物，可斷開更多數目之鍵。可能結果是，在此區域中形成之介電材料在沉積於基板上時可具有減小的流動性或無流動性。隨著基板與淋噴頭之距離增加，交互作用量可略微或更實質地減小。舉例而言，潛在地兩個矽-矽鍵中僅一者或三個矽-矽鍵中僅一者可斷裂，且因此聚合可包括更長鏈之矽基團，此舉可至少部分地給予流動性至沉積材料。
因此，基板可與淋噴頭或前驅物之間開始交互作用的區域維持一距離，亦即小於或約三吋。在所揭示之實施例中，可將基板與淋噴頭維持相距至少0.1吋。亦可將基板維持在小於或約2吋、1吋、0.9吋、0.8吋、0.7吋、0.6吋、0.5吋、0.4吋、0.3吋、0.2吋、0.1吋或更短之一距離，或維持 在約3吋與約0.01吋之間、2吋與0.1吋之間、1吋與0.2吋之間、0.8吋與0.2吋之間等等。亦可結合製程參數及含矽前驅物或正使用之前驅物決定距離。
在沉積製程期間，可在等於或低於約400℃維持基板，且可在等於或低於約300℃、200℃、100℃、80℃、75℃、50℃、25℃、10℃、0℃、-10℃、-20℃、-30℃或更低，在約30℃與-30℃之間等等維持基板。在製程期間可在等於或低於約100托維持處理腔室，且可在等於或低於約50托、25托、15托、5托、1托、0.1托等等或在約0.1毫托與約10托之間維持處理腔室。亦可至少部分地基於含矽前驅物或正使用之前驅物之蒸氣壓設置溫度與壓力。作為一個非限制性實例，若將四矽烷用作含矽前驅物，且腔室溫度為約-10℃，則四矽烷之蒸氣壓可為約3托以下。因此，若腔室壓力大於約3托，則可發生四矽烷之縮聚。電漿流出物與四矽烷之交互作用亦可給予克服縮聚點的能量。另外，隨著與離電漿源之距離增加，及電漿功率在距離或實際產生功率中一者或兩者上減小，可減少矽-矽鍵斷裂量，此舉可允許較長的聚合物鏈形成。改良聚合(亦即，較長矽-矽鏈)與在前驅物之縮聚點處或附近的操作之益處之組合可至少部分地給予流動性至薄膜。製程亦可使用減少的額外材料產生較長的矽聚合物鏈，此舉可減小最終薄膜之收縮量。技術中所使用之電漿源可包括腔室中所產生但遠離基板處理區域及與基板處理區域流體耦接之電漿，或者模組中所產生與處理腔室分離但與處理腔室流體耦接之電漿。電漿可來自任何已知技術或後來發展之 技術，且可產生介於約0與2000瓦特之間的電漿功率。在所揭示之實施例中，電漿功率可小於或約1000瓦特，或約500瓦特、300瓦特、250瓦特、200瓦特、150瓦特、100瓦特、80瓦特、60瓦特、40瓦特、20瓦特等等或更小。
使用所描述之製程，可產生協同組合，在該協同組合中發生一定量縮聚及一定量聚合以自可僅包括矽與氫鍵合之含矽前驅物產生可流動薄膜。合成薄膜在基板上起初形成時可具有流動性，但可主要由矽-矽鍵及矽-氫鍵組成。可在基質中具有更多矽原子及在沉積薄膜中具有更多矽-矽鍵合之該等薄膜可比習知薄膜收縮更少。有利地，發明者已另外決定，該等薄膜在形成時可具有比習知薄膜增加的密度。如此沉積之薄膜可具有大於或等於約1.2g/cc之密度。薄膜亦可具有大於或等於約1.3g/cc、1.4g/cc、1.5g/cc、1.6g/cc、1.7g/cc、1.8g/cc、1.9g/cc、2.0g/cc、2.1g/cc等等或更大之密度。
在基板上已形成一定量介電材料後，可執行額外製程。可執行一或更多個緻密化操作以增加介電材料之品質。在所揭示之實施例中，一旦已形成決定量之介電材料，可停止含矽前驅物之引入及流動。然而，可繼續產生電漿流出物及將該等流出物導入至形成的介電層處之基板處理區域中以緻密化形成的介電材料。或者或另外，可退火形成的矽基介電層以進一步緻密化該薄膜。退火可為乾式退火(諸如使用氮氣)或可在介於約200℃與更高之間、高於或約400℃、高於或約900℃等等或更高溫度下發生之水蒸汽退火。在退火期間，薄膜收縮量可比習知薄膜更少。舉例而言，薄膜在退 火期間可收縮小於50%。另外，由所揭示之技術產生之薄膜可收縮少於或約40%、30%、25%、20%、15%、10%、5%、0%、-5%、-10%等等或更少。在示例性方法及製程中，發明者已決定可發生負收縮。此負收縮可暗示薄膜在處理期間膨脹。
結合第1圖所描述之上述實例製程可產生實質矽基薄膜，且可用於產生各種結構及特性之多晶矽薄膜。可進一步調節製程以合併額外材料以產生氧化物、氮化物、碳化物及在半導體處理中有用之其他組合物。關於第2圖描述所揭示之技術合併額外材料之另一實例。第2圖圖示根據所揭示之實施例形成介電薄膜的製程之另一流程圖。製程可包括關於第1圖所描述之類似操作。在所揭示之實施例中，在操作210處，可將第一前驅物引入至與基板處理區域流體耦接之遠端電漿區域中，同時在遠端電漿區域中形成電漿以產生電漿流出物。第一前驅物可包括任何先前所描述之前驅物中之一或更多者，且可只由諸如氬、氦或氮之一或更多種惰性前驅物組成。在操作220處，可將電漿流出物導入至基板處理區域中。
在操作230處，可將含矽前驅物引入至基板處理區域中，且含矽前驅物可具有至少一個矽-矽鍵。含矽前驅物可包括任何先前所論述之前驅物中之一或更多者。舉例而言，含矽前驅物可具有化學式SixHy，其中x可大於或等於2，且y係2x+n或更大，及其中n可係小於或等於2之任何數字。另外，可將含矽前驅物以實質氣相引入至處理區域中。在所 揭示之實施例中，引入至處理腔室中以形成矽基介電層的前驅物可由一或更多種惰性前驅物及由含有矽-矽鍵及矽-氫鍵組成的含矽前驅物組成。舉例而言，第一前驅物可由氬或氦組成。在操作240處，可使電漿流出物及含矽前驅物反應以在基板上形成矽基介電層。可以先前描述之任何方式執行該等操作。在已形成初始薄膜後，可在操作250處視情況執行固化操作以使用至少一種額外前驅物固化形成的矽基介電層。
額外前驅物可包括諸如臭氧之含氧前驅物、含氮前驅物或含碳前驅物中之一或更多者。可在有或沒有電漿流出物導入至基板處理區域的情況下引入或使用前驅物。可使用額外前驅物另外取代材料進入矽基介電材料。舉例而言，可使用臭氧或另一含氧前驅物以提供氧，將氧合併至矽基質中以產生氧化矽薄膜。此舉可有助於用額外材料包裝形成的基質，使得可進一步在退火或緻密化操作上幫助減少收縮。可以此方式形成各種薄膜，包括氧化物、氮化物、碳化物、氧碳化物、氧氮化物、碳氮化物等等。在矽基介電質之形成後，接近形成之結束時，可使額外前驅物流動及可在有或沒有含矽前驅物及/或第一前驅物的情況下引入額外前驅物。在固化操作期間可改變腔室之溫度及/或壓力。舉例而言，若薄膜形成操作之溫度低於(例如)30℃，則腔室溫度可升高至高於或約30℃、50℃、100℃、200℃等等或更高。
在額外前驅物材料之可選引入後，在操作260處可視情況緻密化固化或以其他方式形成的介電質。可停止含矽 前驅物及/或額外前驅物之流動，及隨後可執行第一前驅物之流動，或在各種實施例中可繼續該流動。可將自第一前驅物中發展的電漿流出物導入至基板處理區域中以緻密化所形成或所固化的介電層。在所揭示之實施例中，可在固化操作前執行緻密化操作，以使得在操作250前執行操作260。在製程中可視情況執行額外操作，包括在操作270處之退火。可如先前所論述退火所形成、固化及/或緻密化的介電質以改良薄膜之最終品質。可執行進一步沉積後處理，該等處理可包括各種操作(包括UV、電子束)及其他固化或退火類型操作中之一或更多者。在退火期間，矽基介電層可收縮少於或約50%。由所揭示之技術產生之薄膜可收縮少於或約40%、30%、25%、20%、15%、10%、5%等等或更少。可在與薄膜形成或沉積操作相同或不同腔室中執行所有可選操作。藉由在不破壞真空的情況下在腔室中維持基板，可減小或防止所形成的薄膜上之濕氣及其他效應。
技術亦包含將含矽前驅物傳遞至遠端電漿區域中。或者，可藉由在腔室之遠端區域中或或者腔室之處理區域中應用之直接電漿活化含矽前驅物，其中將含矽前驅物傳遞至產生電漿之區域中。在所揭示之實施例中，可將含矽前驅物傳遞至腔室之處理區域或電漿區域中及使用諸如先前所界定類型電漿之電漿活化該含矽前驅物。可用諸如惰性載體之額外流體傳遞含矽前驅物，該等流體可包括氬及在所揭示之實施例中亦可包括氫。可在先前所描述之各種溫度、壓力及電漿功率下執行製程。舉例而言，直接施加之電漿功率可小於 500W，及亦可小於或約300W、200W、100W、80W、70W、60W、50W等等或更小，且溫度可低於或約100℃，及亦可低於或約75℃、50℃、25℃、15℃、10℃、5℃、0℃、-5℃等等或更低。另外，在此實施例及其他所揭示之實施例中，可電氣偏壓基板所在基座。基座之偏壓可提供電場，該電場可用於將自由基物質導向至基板之表面。
所描述之製程協同使用具有矽-矽鍵合的含矽前驅物、溫度、壓力、電漿及沉積距離以產生具有改良品質且減少收縮之可流動薄膜。藉由解釋含矽前驅物之相變輪廓，該技術可有利移除氮、碳、水、羥基及可減小形成的薄膜密度及增加形成的薄膜收縮之其他額外材料。如將理解，可使用對腔室參數及電漿功率之額外修改以可視需要進一步調諧沉積製程。有利地，可執行調諧該等製程而無需破壞真空條件或移動基板至額外腔室。此情況比習知技術可減少總體處理時間且節省成本。將在下文描述示例性處理腔室及系統期間揭示沉積製程參數、化學物質及組件之額外實例。
示例性處理系統
可實施本發明之實施例的沉積腔室可包括高密度電漿化學氣相沉積(high-density plasma chemical vapor deposition；HDP-CVD)腔室、電漿增強化學氣相沉積(plasma enhanced chemical vapor deposition；PECVD)腔室、低於大氣壓化學氣相沉積(sub-atmospheric chemical vapor deposition；SACVD)腔室及熱化學氣相沉積腔室，以及其他類型腔室。可實施本發明之實施例的CVD系統之具體實例包括CENTURA ULTIMA® HDP-CVD腔室/系統及PRODUCER® PECVD腔室/系統，以上腔室/系統可購自加州Santa Clara的應用材料公司。
可與本發明之示例性方法使用之基板處理腔室之實例可包括共同受讓之Lubomirsky等人於2006年5月30日提交申請且標題為「PROCESS CHAMBER FOR DIELECTRIC GAPFILL」之美國臨時專利申請案第60/803,499號中所展示及描述之彼等實例，出於所有目的將該臨時專利申請案中之全部內容以引用之方式併入本文。額外示例性系統可包括美國專利案第6,387,207號及第6,830,624號中所展示及描述之彼等系統，亦出於所有目的將該等專利案以引用之方式併入本文。
第3A圖圖示根據所揭示之技術之基板處理腔室301的一部分之示意性橫截面圖。遠端電漿系統(remote plasma system；RPS)310可處理氣體，該氣體隨後移動穿過氣體入口組件311。可在氣體入口組件311內部存在兩個不同氣體供應通道。第一通道312可載送氣體穿過遠端電漿系統(RPS)310，而第二通道313可繞過RPS 310。在所揭示之實施例中，第一通道312可用於製程氣體且第二通道313可用於處理氣體。圖示絕緣環324安置在蓋或導電頂部部分321與諸如淋噴頭353之多孔分隔之間，此情況可允許將交流電位相對於淋噴頭353施加至蓋321上。製程氣體可移動穿過第一通道312至腔室電漿區域320中及可藉由腔室電漿區域320中之電漿單獨或與RPS 310組合激勵該製程氣體。腔室電漿區域320及/或RPS 310之組合在本文中可稱為遠端電漿系統。多孔分隔或淋 噴頭353可將腔室電漿區域320與淋噴頭353下的基板處理區域370分離。淋噴頭353可允許腔室電漿區域320中存在之電漿避免直接激勵基板處理區域370中的氣體，同時仍允許經激勵之物質自腔室電漿區域320移動至基板處理區域370中。
可將淋噴頭353定位於腔室電漿區域320與基板處理區域370之間，且允許電漿流出物或前驅物之激勵衍生物或腔室電漿區域320內部所產生之其他氣體穿過複數個通孔356，該等通孔橫貫淋噴頭中所包括之平板或多個平板之厚度。淋噴頭353亦可具有一或更多個中空體積351，該等中空體積可充滿蒸氣或氣體形式之前驅物(諸如含矽前驅物)及穿過小孔355到達基板處理區域370中，而非直接到達腔室電漿區域320中。在所揭示之實施例中，淋噴頭353可比通孔356之最小直徑350之長度更厚。為了維持自腔室電漿區域320穿透至基板處理區域370之激勵物質之明顯濃度，可藉由形成部分穿透淋噴頭353的通孔356之較大直徑部分來限制通孔之最小直徑350之長度326。在所揭示之實施例中，通孔356之最小直徑350之長度可為與通孔356之最小直徑相同的數量級或更小。
在所示之實施例中，淋噴頭353可經由通孔356分配製程氣體，該等製程氣體含有諸如(例如)氬之電漿蒸氣/氣體。另外，淋噴頭353可經由較小孔355分配含矽前驅物，將該含矽前驅物與電漿區域320保持分離。可經由淋噴頭353保持製程氣體或多個製程氣體與含矽前驅物流體分離，直至 前驅物單獨進入處理區域370。前驅物一旦進入處理區域便可彼此接觸及反應以在基板380上形成可流動介電材料。
在實施例中，通孔356之數目可介於約60與約2000之間。通孔356可具有各種形狀但可製成圓形。在所揭示之實施例中，通孔356之最小直徑350可介於約0.5mm與約20mm之間或介於約1mm與約6mm之間。選擇通孔之橫截面形狀中亦存在範圍，該橫截面可製成圓錐形、圓柱形或兩個形狀之組合。用於將氣體引入至基板處理區域370中的小孔355之數目在不同實施例中可介於約100與約5000之間或介於約500與約2000之間。小孔355之直徑可介於約0.1mm與約2mm之間。
第3B圖圖示根據所揭示之技術之淋噴頭353之仰視平面圖。淋噴頭353對應於第3A圖中所示之淋噴頭。描述通孔356在淋噴頭353之底部上具有較大內直徑(inner-diameter；ID)及在頂部上具有較小ID。小孔355實質上均勻分佈於淋噴頭之表面上，甚至在通孔356中間，此舉可有助於提供比本文所描述之其他實施例更加均勻之混合。
在2011年10月3日提交申請之專利申請案第13/251,714號中更加完整地描述額外雙通道淋噴頭以及此處理系統及腔室，出於所有目的將該申請案以引用之方式併入本文以達到與本文所主張之特徵及描述相一致的程度。
當穿過淋噴頭353中的通孔356到達之電漿流出物與發源自中空體積351之穿過小孔355到達之含矽前驅物組合時，可在由基板處理區域370內之基座(諸如上面安置有 基板380的基座375)支撐的基板上產生示例性薄膜。儘管可配備基板處理區域370以支援電漿用於諸如固化之其他製程，但是在示例性薄膜之生長或沉積期間可不存在電漿。
可在淋噴頭353上方的腔室電漿區域320或淋噴頭353下方的基板處理區域370點燃電漿。或者，可在腔室之任何部分中不形成電漿及僅可在RPS單元310中形成電漿。可在腔室電漿區域320中存在電漿以諸如自氬、氦、氫或氨中之一或更多者之流入物產生自由基電漿流出物。在處理腔室之導電頂部部分(諸如蓋321)與淋噴頭353之間施加通常在射頻(radio frequency；RF)範圍內的交流電壓以在沉積期間點燃腔室電漿區域320中的電漿。RF電源產生13.56百萬赫之高RF頻率，但亦可單獨或與13.56百萬赫頻率組合產生其他頻率。
當在介電層之形成期間可開啟基板處理區域370中的底部電漿時或在清洗基板處理區域370邊界處之內表面的同時，可將頂部電漿保持處於低功率或無功率。可藉由在淋噴頭353與腔室之基座375或底部之間施加交流電壓來點燃基板處理區域370中的電漿。可在存在電漿的同時將清洗氣體引入至基板處理區域370中。
基座375可為可移動的，及在所揭示之實施例中該基座可經配置以升高或降低，及該基座可經類似地配置以旋轉。基座375可具有熱交換通道，熱交換流體流動穿過該通道以控制基板之溫度。此配置允許基板溫度經冷卻或加熱以維持相對低溫，諸如約0℃或更低至約200℃或更高。熱交 換流體可包含乙二醇、水或能夠引入熱量或自系統移除熱量之一些其他流體。亦可電阻加熱基座之晶圓支撐圓盤以便使用嵌入電阻加熱元件實現約200℃或更低至約1100℃或更高之相對高溫。可與支撐圓盤之周邊相鄰佈置加熱器元件之外部部分，同時在具有較小半徑的同心圓之路徑上佈置內部部分。可另外經由圓盤盤繞電阻加熱元件以提供更加均勻的溫度。至加熱器元件的電線可穿過基座之桿。
腔室電漿區域或RPS中的區域可稱為遠端電漿區域。在實施例中，可在遠端電漿區域產生自由基前驅物(例如，氬前驅物)且該自由基前驅物移動至基板處理區域中以與含矽前驅物組合。在實施例中，僅藉由氬自由基前驅物激勵含矽前驅物。在實施例中，可將電漿功率基本上僅施加至遠端電漿區域，以確保氬自由基前驅物提供對含矽前驅物的主要激勵。
在使用腔室電漿區域之實施例中，可在與沉積區域分隔之基板處理區域之截面中產生經激勵之電漿流出物。沉積區域(在本文中亦稱為基板處理區域)可為電漿流出物與含矽前驅物混合及反應以在基板(例如，半導體晶圓)上沉積介電材料之區域。經激勵之電漿流出物亦可伴隨有包括(例如)其他惰性氣體或氨的額外氣體。在實施例中，含矽前驅物在進入基板電漿區域前可不穿過電漿。在介電材料之沉積期間，基板處理區域在本文中可描述為「無電漿」。「無電漿」不一定意謂該區域缺乏電漿。在電漿區域內產生的遊離物質及自由電子可移動穿過分隔或淋噴頭中的微孔或孔，但 不可實質上藉由施加至電漿區域之電漿功率激勵含矽前驅物。腔室電漿區域中電漿之邊界難以界定及電漿可穿過淋噴頭中的孔侵佔基板處理區域。在電感耦合電漿的情況下，可直接在基板處理區域內實現少量遊離。此外，可在沒有消除形成薄膜之理想特徵的情況下在基板處理區域中產生低強度電漿。在經激勵之電漿流出物之產生期間電漿之強度離子密度比腔室電漿區域或遠端電漿區域低得多的所有原因不脫離本文所使用之「無電漿」之範疇。
電漿功率可為各種頻率或多個頻率之組合。在示例性處理系統中，可藉由相對於淋噴頭353傳遞至蓋321的RF功率提供電漿。在不同實施例中，RF功率可介於約10瓦特與約2000瓦特之間、介於約100瓦特與約2000瓦特之間、介於約200瓦特與約1500瓦特之間、小於或約100瓦特或小於或約500瓦特。在不同實施例中，在示例性處理系統中施加的RF頻率可為小於約200千赫的低RF頻率、介於約10百萬赫與約15百萬赫之間的高RF頻率或大於或約1十億赫的微波頻率。可將電漿功率電容耦合(capacitively-coupled；CCP)或電感耦合(inductively-coupled；ICP)至遠端電漿區域中。
在前驅物、任何載氣及電漿流出物流動進入基板處理區域370期間，可將基板處理區域370維持在各種壓力下。在不同實施例中，壓力可維持在約0.1毫托與約100托之間、在約1托與約20托之間、小於約5托或小於約3托。
可將沉積系統之實施例合併至較大製造系統中以便 產生積體電路晶片。第3圖圖示根據所揭示之實施例的沉積、蝕刻、烘焙及固化腔室之一個此類系統400。在圖式中，一對前端開口晶圓盒(front opening unified pods；FOUPs)402供應各種大小之基板，該等基板由機器人臂404接收及放置到低壓固持區域406中，隨後再放置到基板處理腔室408a至408f之一者中。可使用第二機器人臂410以將基板晶圓自固持區域406傳送至基板處理腔室408a至408f及返回。可配置每個基板處理腔室408a至408f以執行眾多基板處理操作，該等處理操作除循環層沉積(cyclical layer deposition；CLD)、原子層沉積(atomic layer deposition；ALD)、化學氣相沉積(chemical vapor deposition；CVD)、物理氣相沉積(physical vapor deposition；PVD)、蝕刻、預清洗、脫氣、定向及其他基板製程外還包括本文所描述之沉積製程。
基板處理腔室408a至408f可包括一或更多個系統組件用於在基板晶圓上沉積、退火、固化及/或蝕刻介電薄膜。在一配置中，可使用兩對處理腔室(例如，處理腔室408c-408d及處理腔室408e-408f)以在基板上沉積介電材料，及可使用第三對處理腔室(例如，處理腔室408a-408b)以蝕刻經沉積之介電質。在另一配置中，可配置所有三對腔室(例如，腔室408a至408f)以在基板上沉積、固化及緻密化介電薄膜。可在與不同實施例中所示之製造系統分離的一或多個腔室中實施所描述之製程中的任一或更多者。
在先前描述中，出於解釋之目的，已闡述眾多細節以便提供對本發明之各種實施例之理解。然而，對熟習此項 技術者將顯而易見的是，可在沒有該等細節中之一些細節或具有額外細節的情況下實施某些實施例。
已揭示若干實施例，熟習此項技術者將認識到，在不脫離所揭示之實施例之精神的情況下可使用各種修改、替代結構及等效物。另外，並未描述眾多熟知製程及元件以免不必要地模糊本發明。因此，不應將上文描述視為限制本發明之範疇。
在提供值範圍的情況下，應理解，亦具體揭示介於彼範圍之上限與下限之間的每個中間值(精確到下限單位的最小分數)，除非上下文另有清楚指示。包含在所述範圍中的任何所述值或中間值與彼所述範圍中的任何其他所述值或中間值之間的每個較小範圍。彼等較小範圍之上限及下限可獨立被包括或不包括在該範圍內，且本發明中亦包含較小範圍內包括上限與下限中一者、不包括上限與下限兩者或包括上限與下限兩者之每個範圍。在所述範圍包括上限與下限中之一者或兩者的情況下，亦包括不包括彼等所包括上限與下限中之一者或兩者的範圍。
如本文所使用及在隨附申請專利範圍中所使用，除非上下文另有清楚指示，否則單數形式之「一(a)」、「一(an)」及「該」包括複數引用。因此，例如，對「一孔」之引用包括複數個此類孔，及對「該平板」之引用包括引用一或更多個平板及為熟習此項技術者所知的平板等效物等等。
又，當在本說明書及以下申請專利範圍中使用時，字詞「包含(comprise(s))」、「包含(comprising)」、「含有 (contain(s))」、「含有(containing)」、「包括(include(s))」及「包括(including)」意欲指定所述特徵、整數、組件或步驟之存在，但並未排除一或更多個其他特徵、整數、組件、步驟、行為或群組之存在或添加。
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Claims (20)

  1. 一種在一處理腔室之一基板處理區域中的一基板上形成一介電層之方法，該方法包含以下步驟：將一第一前驅物引入至與該基板處理區域流體耦接之一遠端電漿區域中，同時在該遠端電漿區域形成一電漿以產生電漿流出物；將該等電漿流出物導入至該基板處理區域中；將一含矽前驅物引入至該基板處理區域中，其中該含矽前驅物包括至少一個矽-矽鍵；以及在該基板處理區域中使該等電漿流出物及含矽前驅物反應以形成一矽基介電層，該介電層在該基板上形成時起初為可流動的。
  2. 如請求項1所述之方法，其中該含矽前驅物包括至少兩個矽-矽鍵。
  3. 如請求項1所述之方法，其中該第一前驅物包括選自由氨、氮、H2、Ar及He組成之群組中的一或更多種前驅物。
  4. 如請求項1所述之方法，其中經由一淋噴頭將該等電漿流出物及含矽前驅物引入至該處理區域中，該淋噴頭經配置以維持該等前驅物之分離，使得該等前驅物在進入該基板處理區域前不彼此接觸。
  5. 如請求項4所述之方法，其中維持該基板與該淋噴頭相隔小於或約3吋之一距離。
  6. 如請求項1所述之方法，其中該基板處理區域在該沉積製程期間為無電漿。
  7. 如請求項1所述之方法，其中該含矽前驅物具有化學式SixHy，其中x係大於或等於2，且y係2x+n或更大，其中n係小於或等於2的任何數字，且其中將該含矽前驅物以一實質氣相引入至該處理區域中。
  8. 如請求項1所述之方法，其中在小於或等於約30℃之一溫度下執行該方法。
  9. 如請求項1所述之方法，其中在小於或等於約5托之一壓力下執行該方法。
  10. 如請求項1所述之方法，其中該如此形成之薄膜具有大於或等於約1.4g/cc之一密度。
  11. 如請求項1所述之方法，該方法進一步包含以下步驟：在形成該矽基介電層後停止該含矽前驅物之該引入，及將該等電漿流出物導入至該基板處理區域中以緻密化該形成的介電層。
  12. 如請求項1所述之方法，該方法進一步包含以下步驟：退火該形成的矽基介電層。
  13. 如請求項12所述之方法，其中在該退火之步驟期間該形成的矽基介電層收縮小於約20%。
  14. 一種在一處理腔室之一基板處理區域中的一基板上形成一介電層之方法，該方法包含以下步驟：將一第一前驅物引入至與該基板處理區域流體耦接之一遠端電漿區域中，同時在該遠端電漿區域形成一電漿以產生電漿流出物；將該等電漿流出物導入至該基板處理區域中；將一含矽前驅物引入至該基板處理區域中，其中該含矽前驅物包括至少一個矽-矽鍵；在該基板處理區域中使該等電漿流出物及含矽前驅物反應以形成一矽基介電層，該介電層在該基板上形成時起初為可流動的；以及使用至少一種額外前驅物固化該形成的矽基介電層。
  15. 如請求項14所述之方法，其中該至少一種額外前驅物包含一含氧前驅物、一含氮前驅物或一含碳前驅物。
  16. 如請求項14所述之方法，該方法進一步包含以下步驟：將該等電漿流出物導入至該基板處理區域中以緻密化該固化的介電層。
  17. 如請求項14所述之方法，其中該含矽前驅物具有該化學式SixHy，其中x係大於或等於2，且y係2x+n或更大，其中n係小於或等於2的任何數字，且其中將該含矽前驅物以一實質氣相引入至該處理區域中。
  18. 如請求項14所述之方法，其中引入至該處理腔室中以形成該矽基介電層的該等前驅物由一或更多種惰性前驅物及由含有矽-矽鍵及矽-氫鍵組成的一含矽前驅物組成。
  19. 如請求項14所述之方法，該方法進一步包含以下步驟：退火該形成的矽基介電層。
  20. 如請求項14所述之方法，其中在該退火之步驟期間該形成的矽基介電層收縮小於約20%。
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