TWI625418B - 用於原子層沈積之溶液爲主前驅物的直接液體注射 - Google Patents
用於原子層沈積之溶液爲主前驅物的直接液體注射 Download PDFInfo
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Abstract
本發明係關於用於ALD製程中之精確控制溶液為主前驅物之輸送的系統及方法。藉由利用前驅物溶液之直接液體注射至局部汽化器中可精確控制溶液為主前驅物之汽化及汽化前驅物之輸送，以便利用轉換型ALD工具達成真正之ALD膜生長。
Description
本發明係關於用於原子層沈積製程中之輸送及汽化溶液為主前驅物的方法及系統。
莫耳定律(Moore's law)預示著低廉存在於積體電路上之電晶體數目大致每兩年便發生倍增的長期趨勢。數位電子器件之性能，例如處理速度、記憶容量等在過去半個世紀已與莫耳定律密切相關且預期還要持續數年。
然而，隨著半導體器件愈來愈緻密地被符合莫耳定律之器件堆填，通道長度須製得愈來愈小且須增強晶片效能，同時降低單位成本。為滿足該等需求，需要開發及使用結合矽為主IC晶片使用之新材料。舉例而言，已提出在電子器件之關鍵功能部位中使用過渡金屬及鑭系金屬。該等金屬之氧化物可用於替代當前之SiO2及SiON閘極介電質，因為該等氧化物可沈積為超薄、有效氧化物厚度低於1.5nm、高k之氧化物。具有可接受之特性(諸如高能帶間隙及能帶偏移、矽上之優良穩定性、最小SiO2界面層及基板上之高品質界面)之高k材料的實例描述於公開之美國專利申請案20100055321及已頒佈美國專利7,514,119中，各案以引用之方式併入本文中。適用於沈積該等高k材料之前驅物的更多特定實例描述於公開之美國專利申請案
20090305504、公開之美國專利申請案20090117274、公開之美國專利申請案20100290945、公開之美國專利申請案20100290968及公開之PCT專利申請案2011005653中，各案以引用之方式併入本文中。
原子層沈積(ALD)為賦能沈積技術，用於下一代導體障壁層；矽、鍺及碳為主之第IV族元素半導體之高k閘極介電質層；InGaAs及其他第III-V族高電子遷移率半導體之高k閘極介電質層；碳為主之電子器件的高k閘極介電質層，諸如碳奈米管及石墨烯應用；用於DRAM之高k電容器層；用於快閃及鐵電記憶器件之高k介電質層；用於STT-MRAM之磁接合層；相變記憶體及電阻式RAM記憶體中之功能層；用於氣體純化、有機合成、燃料電池膜及化學偵測器之金屬為主觸媒層；用於燃料電池中之電極材料的金屬為主表面；覆蓋層；金屬閘電極等。然而，以上參考案所提及之多種前驅物可能難以用於諸如ALD之氣相沈積製程中，因為該等前驅物通常具有低揮發性且在室溫下以固體存在。因此，如上述參考案所提及，前驅物材料必須與適合溶劑合併以產生溶液為主前驅物隨後用於沈積製程中。ALD處理為用於沈積該等溶液為主前驅物之最有益的技術，因為ALD係用於在循環沈澱製程中由一次性產生之單層積聚成金屬、氧化物、氮化物及其他物之超薄高保形層。ALD製程亦可適用於製造平板顯示器、複合半導體、磁性及光學儲存器件、太陽電池、奈米技術及奈米材料。
典型之ALD製程使用依序前驅物氣體脈衝沈積膜，一次一層。特定言之，將第一前驅物氣體引入製程室中且在室中藉由基板表面之反應產生單層。隨後引入第二前驅物以與第一前驅物反應且在基板上形成由第一前驅物與第二前驅物組分組成之單層膜。各對脈衝(一個循環)精確地產生膜之一個單層，從而基於沈積循環進行之次數而精確控制最終膜厚度。
如以上提及之參考案所述，對於ALD製程，前驅物應具有優良之
揮發性且能夠經由化學吸附及表面反應而使基板表面迅速飽和。ALD半反應循環應在5秒內完成，較佳在1秒內，且暴露量應低於108朗繆爾(Langmuir)(1Torr*sec=106Langmuir)。前驅物本身亦應具高活性以使表面反應快速且完全，因為完全反應在所產生之膜中得到優良之純度。由於該等溶液為主前驅物之沈積參數需要重要的控制，因此輸送及汽化機構具重要作用。所用設備及技術必須能夠在沈積溫度窗內保持溶液為主前驅物材料之穩定性以免CVD反應不可控。
一般而言，標準商業輸送及汽化系統不適合於溶液為主前驅物。此部分係因為難以輸送為限制基板之單層覆蓋所需的足夠少量前驅物。特定言之，氣相反應物之脈衝寬度為1秒或小於1秒且汽化液體脈衝形狀可因汽化後損失之液體脈衝之尖銳前緣及尾緣而畸變。極難使兩種完全分離之反應物同步進行所需之自限及依序ALD生長。
舉例而言，得自Cambridge NonoTech之SavannahTM系列ALD系統為可用ALD系統之代表。此系統提供利用靜態單端源容器將ALD膜沈積於200mm晶圓表面上的方法。藉由得自Swagelok之ALD脈衝閥輸送壓力高於腔室操作壓力之純前驅物蒸氣。為達到足夠高的前驅物蒸氣壓，單端源溶器可藉由具有溫控之電加熱夾套加熱。然而，在標準Savannah ALD工具中難以使用溶液為主前驅物，因為在控制溫度下，在脈衝期間，溶液為主前驅物中之溶劑及溶質在氣相中分離。高揮發性組分(一般為溶劑)因此富集在源容器之頂隙中，導致沈積不一致。
直接液體注射法可用於控制前驅物材料之汽化及脈衝。美國公開之專利申請案2003/0056728揭示一種在原子氣相沈積(AVD)製程中使用呈液體或溶解形式之前驅物的液體脈衝注射方法。然而，液體量太大而不能滿足ALD生長需要。Min等人「Atomic layer deposition of Al2O3 thin films from a 1-methoxy-2-methyl-2-propoxide complex of
aluminum and water」，Chemistry Materials(2005)描述一種用於溶液前驅物之液體脈衝方法，其中用於ALD生長之液體量又太大而不能發生。該等液體脈衝方法均無法提供ALD生長，而是代表CVD製程的變化形式且導致CVD層生長不可控。
與ALD製程中溶液為主前驅物之汽化及輸送相關之方法及裝置係描述於公開之美國專利申請案20100036144及公開之美國專利申請案20100151261中，二者均以引用之方式併入本文中。
此項技術中仍需要改良ALD溶液為主前驅物之輸送及汽化。特定言之，需能夠使用配合現存商業ALD晶圓工具之局部汽化器。
本發明提供用於將溶液為主前驅物輸送至與標準ALD晶圓工具整合之局部汽化器中的方法及系統。更特定言之，本發明提供方法及系統，其中溶液為主前驅物之輸送及汽化係如下精確控制：使前驅物液體脈衝至局部汽化器內、使脈衝至局部汽化器內之液體完全汽化、使完全汽化之前驅物經氣相ALD脈衝至沈積室內及使清潔惰性氣體脈衝類似地脈衝至該腔室內。此製程達成真正可控之ALD膜生長。液體脈衝可為來自無任何怠體積之雙重源Flex-ALD容器之溶液為主前驅物或清潔溶劑。
10‧‧‧溶液為主前驅物源容器
20‧‧‧局部汽化器
30‧‧‧標準ALD晶圓工具前驅物歧管/晶圓沈積室
40‧‧‧液體質量流量控制器
50‧‧‧液體脈衝閥
60‧‧‧惰性氣體源
70‧‧‧氣體質量流量控制器
80‧‧‧氣體脈衝閥
85‧‧‧背壓調節器
90‧‧‧蒸氣脈衝閥
100‧‧‧溶液為主前驅物輸送系統
200‧‧‧ALD沈積系統
210‧‧‧第一溶液為主前驅物輸送系統
220‧‧‧第一局部汽化器
225‧‧‧第一蒸氣脈衝閥
230‧‧‧沈積室
235‧‧‧入口
238‧‧‧排氣口
240‧‧‧第二溶液為主前驅物輸送系統
250‧‧‧第二局部汽化器
255‧‧‧第二蒸氣脈衝閥
260‧‧‧標準單端源容器
265‧‧‧閥
270‧‧‧標準單端源容器
275‧‧‧閥
圖1為根據本發明之一個實施例之ALD沈積系統的示意圖。
圖2為根據本發明之另一實施例之ALD沈積系統的示意圖。
圖3A、3B及3C為展示用於本發明系統操作之脈衝次序的時間圖。
本發明提供用於ALD製程中之精確控制溶液為主前驅物之輸送的方法及系統。藉由利用前驅物溶液直接液體注射至局部汽化器中可精
確控制溶液為主前驅物之汽化及汽化前驅物之輸送以達成真正之ALD膜生長。
本發明之系統提供一種在標準ALD晶圓工具上藉由直接液體注射將溶液為主液體前驅物引入局部汽化器中之方法。溶液為主前驅物係在室溫下藉由液體質量流量控制來傳輸，以使前驅物材料具有低熱量預算且防止前驅物之任何熱降解。溶液為主前驅物隨後在局部汽化器內汽化而得到用於ALD操作之氣相前驅物及溶劑蒸氣。本發明之系統可嵌入式置換標準靜態加熱源容器且不需要修改沈積室或前驅物歧管。。
本發明之系統將參考附圖作更加詳細地描述。特定言之，圖1為具有局部汽化器之溶液為主前驅物輸送系統100之示意圖，該系統包含與局部汽化器20連通的溶液為主前驅物源容器10，該局部汽化器容納在標準ALD晶圓工具前驅物歧管30內。容器10與汽化器20之間的連通經過液體質量流量控制器40及液體脈衝閥50。惰性氣體源60亦經由氣體質量流量控制器70及氣體脈衝閥80而與汽化器20連通且可利用背壓調節器85調節。系統100亦包括連接至汽化器20之出口之蒸氣脈衝閥90。
溶液為主前驅物輸送系統100根據以下方法操作。製備溶液為主前驅物材料，諸如在本申請案之【先前技術】章節中所提及之若干公開專利申請案及已頒佈專利中所描述之前驅物材料。將所製備之溶液為主前驅物填充至容器10之內部容器中，該容器可為雙重ALD起泡容器，諸如在公開之美國專利申請案2010/0140120中所描述者，該申請案以引用之方式併入本文中。將諸如辛烷之純溶劑填充至容器10之外部容器中。使用此類容器10可輸送待切換以輸送至汽化器20之純溶劑或前驅物溶液而無需斷開管線。利用液體質量流量控制器40及液體脈衝閥50謹慎地控制輸送至汽化器之溶劑或前驅物溶液。質量流量控制
器40較佳為低△T液體質量流量控制器，其中輸送材料之溫度升高或降低低於5℃且較佳低於3℃。此控制避免氣泡之形成且亦避免輸送材料之組分分離，以及在液體輸送管線中減少氣泡之形成。液體脈衝閥50將精確控制量之液體在室溫下輸送至汽化器20中。汽化器20可由不鏽鋼建構且可包括VCR連接以及內建式液體注射噴嘴。輸送至汽化器20之液體前驅物溶液隨後在高達250℃之溫度下，較佳在100℃至200℃之溫度下藉由汽化器20完全汽化，而不發生相分離。若欲加壓汽化前驅物，則可將來自惰性氣體源60之惰性氣體與前驅物溶液一起輸送至汽化器20。惰性氣體經由氣體質量流量控制器70及氣體脈衝閥80以經控制量輸送且藉由調節器85調節背壓。一旦前驅物材料已汽化，則前驅物材料即經由蒸氣脈衝閥90以精確控制之方式輸送至晶圓沈積室30。此精確控制使得前驅物蒸氣在無前緣及尾緣形成之情況下輸送。沈積之後，晶圓室可用惰性氣體沖洗。
圖2為具有本發明之溶液為主前驅物輸送系統(諸如圖1中所示者)之ALD沈積系統200的示意圖。在ALD系統200中，採用一個以上前驅物源容器。特定言之，第一溶液為主前驅物輸送系統210與第一局部汽化器220及第一蒸氣脈衝閥225連通用於經由入口235將前驅物材料輸送至沈積室230。第二溶液為主前驅物輸送系統240與第二局部汽化器250及第二蒸氣脈衝閥255連通用於經由入口235將另一前驅物材料輸送至沈積室230。另外，其他反應物，諸如去離子水(DI water)或純液體前驅物可儲存在標準單端源容器中，諸如容器260及容器270，以便經由與腔室入口235連通之各別閥265及閥275將該等反應物輸送至沈積室230。未反應之處理材料經由排氣口238排出腔室230。系統200提供本發明之所有益處，以及沈澱操作中更大程度之變通性以及對前驅物及其他反應物材料之更大程度的選擇。
用於ALD系統200之單操作次序包含將第一前驅物材料輸送至第
一局部汽化器220汽化，隨後以精確控制之脈衝形式經由第一蒸氣脈衝閥225輸送至沈積室230。為完成ALD循環，隨後將將第二前驅物材料輸送至第二局部汽化器250以汽化，隨後以精確控制之脈衝形式經由第二蒸氣脈衝閥255輸送至沈積室230。沖洗步驟可在兩次前驅物輸送之前、之間及之後添加。在一個替代方案中，並未使用第二溶液為主前驅物，而代之以純液體前驅物且自例如容器260或容器270輸送出。另一實施例提供添加第三溶液為主前驅物材料，其經由第三汽化器輸送至沈積室。或者，第三前驅物材料可為自標準容器輸送之純液體前驅物。
圖3A、3B及3C為展示本發明之系統操作之脈衝次序的時間圖。特定言之，圖3A為圖1中所示之系統100之閥50、閥80及閥90之操作的時間圖。如圖所示，打開液體脈衝閥50以將液體前驅物脈衝至汽化器。視情況而定，隨後打開氣體脈衝閥80以使惰性氣體脈衝至汽化器以加壓前驅物蒸氣。汽化之後，打開蒸氣脈衝閥90以將汽化前驅物材料輸送到沈積室。隨後重複閥操作次序直至達成所需之膜沈積厚度。
圖3B為圖1中所示之系統100之閥50、閥80及閥90之操作的時間圖且包括汽化器預清潔。如圖所示，打開氣體脈衝閥80以將沖洗氣體送至汽化器。隨後打開液體脈衝閥50以將液體前驅物脈衝至汽化器。視情況而定，再次打開氣體脈衝閥80以將惰性氣體脈衝至汽化器以加壓汽化前驅物。汽化之後，打開蒸氣脈衝閥90以將汽化前驅物材料輸送到沈積室。隨後重複閥操作次序直至達成所需之膜沈積厚度。
圖3C為圖1中所示之系統100之閥50、閥80及閥90之操作的時間圖且包括後清潔。如圖所示，打開液體脈衝閥50以將液體前驅物脈衝至汽化器。汽化之後，打開蒸氣脈衝閥90以將汽化前驅物材料輸送到沈積室。隨後打開氣體脈衝閥80以將沖洗氣體送至汽化器且再次打開蒸氣脈衝閥90以將沖洗氣體送至沈積室用於清潔。隨後重複閥操作次
序直至達成所需之膜沈積厚度。
本發明提供ALD沈積製程之極精確控制。表1闡述利用本發明之系統獲得之膜的兩個實例。
預期熟習此項技術者依據以上說明將顯而易知本發明之其他實施例及變化，且希望如隨附申請專利範圍所述之本發明範疇內同樣包括該等實施例及變化。舉例而言，可利用多種不同管道及閥配置而不背離本發明。此外，容器及容器內腔室之幾乎任何配置均為可能的。舉例而言，氣罐配置內可存在僅需要單一惰性氣體進料的氣罐以便加壓兩個腔室之頂隙。
Claims (20)
- 一種用於原子層沈積之系統，其包含：ALD沈積室；前驅物歧管，其與該沈積室連通且容納具有蒸氣脈衝閥之汽化器；溶液為主前驅物源容器，其經由液體質量流量控制器及液體脈衝閥而與該汽化器連通；及惰性氣體源容器，其經由氣體質量流量控制器及氣體脈衝閥而與該汽化器連通。
- 如請求項1之系統，其中該溶液為主前驅物源容器為具有兩個分離室之容器。
- 如請求項1之系統，其中該液體質量流量控制器為低△T液體質量流量控制器。
- 如請求項1之系統，其中經由該液體質量流量控制器引起之溫度升高或降低低於5℃。
- 如請求項1之系統，其中經由該液體質量流量控制器引起之溫度升高或降低低於3℃。
- 如請求項1之系統，其中該汽化器係在高達250℃之溫度下操作。
- 如請求項1之系統，其中該汽化器係在100℃與200℃之間的溫度下操作。
- 如請求項1之系統，其進一步包含與該惰性氣體源容器與該汽化器之間之連通相關之背壓調節器。
- 如請求項1之系統，其進一步包含經由第二液體質量流量控制器及第二液體脈衝閥而與第二汽化器連通之第二溶液為主前驅物源容器。
- 如請求項1之系統，其進一步包含經由閥而與該沈積室連通之至少一個反應物源容器。
- 一種用於原子層沈積之方法，其包含：經由第一液體質量流量控制器及第一液體脈衝閥將第一溶液為主前驅物之精確控制脈衝自第一前驅物源容器輸送至第一汽化器；在該汽化器中汽化該前驅物；經由蒸氣ALD閥將該汽化前驅物脈衝輸送至ALD沈積室，該脈衝具有含有圓滑前緣及尾緣之方波，如前驅物蒸氣量；輸送沖洗氣體至少通過該沈積室；經由蒸氣ALD閥將第二前驅物輸送至該ALD沈積室，該脈衝具有含有圓滑前緣及尾緣之方波，如前驅物蒸氣量；輸送沖洗氣體至少通過該沈積室；及重複以上該等步驟直至該所需厚度之膜在該沈積室中沈積於基板上。
- 如請求項11之方法，其中汽化係在高達250℃之溫度下進行。
- 如請求項11之方法，其中該汽化係在100℃與200℃之間的溫度下進行，該溫度經選擇而與汽化之該溶液為主前驅物之該調配物一致。
- 如請求項11之方法，其進一步包含將精確控制量之來自惰性氣體源的惰性氣體以及該溶液為主前驅物輸送至該汽化器之後，經由氣體質量流量控制器及氣體脈衝閥輸送該惰性氣體，該惰性氣體有助於該汽化前驅物脈衝之輸送。
- 如請求項11之方法，其中輸送第二前驅物包含將反應物氣體輸送至該沈積室。
- 如請求項11之方法，其中輸送第二前驅物包含： 經由第二液體質量流量控制器及第二液體脈衝閥將第二溶液為主前驅物之精確控制脈衝自第二前驅物源容器輸送至第二汽化器；在該第二汽化器中汽化該第二前驅物；及經由第二蒸氣ALD閥將該第二汽化前驅物脈衝輸送至該ALD沈積室，該第二脈衝具有含有圓滑前緣及尾緣之方波，如前驅物蒸氣量。
- 如請求項11之方法，其進一步包含將第三前驅物輸送至該ALD沈積室。
- 如請求項17之方法，其中輸送第三前驅物包含將反應物氣體輸送至該沈積室。
- 如請求項17之方法，其中輸送第三前驅物包含：經由第三液體質量流量控制器及第三液體脈衝閥將第三溶液為主前驅物之精確控制脈衝自第三前驅物源容器輸送至第三汽化器；在該第三汽化器中汽化該第三前驅物；及經由第三蒸氣ALD閥將該第三汽化前驅物脈衝輸送至該ALD沈積室，該第三脈衝具有含有圓滑前緣及尾緣之方波，如前驅物蒸氣量。
- 如請求項11之方法，其進一步包含在輸送該第一溶液為主前驅物之前，輸送沖洗氣體通過該第一汽化器及該沈積室。
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| TW (1) | TWI625418B (zh) |
| WO (1) | WO2014039597A2 (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI505986B (zh) * | 2013-01-10 | 2015-11-01 | Nat Tsing Hua Unioversity | 石墨烯製備系統及方法 |
| US9515155B2 (en) * | 2013-12-20 | 2016-12-06 | Globalfoundries Inc. | E-fuse design for high-K metal-gate technology |
| US9524962B2 (en) | 2013-12-20 | 2016-12-20 | Globalfoundries Inc. | Semiconductor device comprising an e-fuse and a FET |
| US9466685B2 (en) | 2015-02-23 | 2016-10-11 | Globalfoundries Inc. | Semiconductor structure including at least one electrically conductive pillar, semiconductor structure including a contact contacting an outer layer of an electrically conductive structure and method for the formation thereof |
| WO2024050252A1 (en) * | 2022-09-02 | 2024-03-07 | Lam Research Corporation | Atomic layer deposition with in-situ sputtering |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200506093A (en) * | 2003-04-21 | 2005-02-16 | Aviza Tech Inc | System and method for forming multi-component films |
| WO2006023501A2 (en) * | 2004-08-16 | 2006-03-02 | Aviza Technology, Inc. | Direct liquid injection system and method for forming multi-component dielectric films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100129548A1 (en) * | 2003-06-27 | 2010-05-27 | Sundew Technologies, Llc | Ald apparatus and method |
| CN101684550B (zh) * | 2004-06-28 | 2012-04-11 | 剑桥纳米科技公司 | 设计为用于气相沉积系统中的阱 |
| KR20090038461A (ko) * | 2006-07-21 | 2009-04-20 | 린드 인코포레이티드 | 원자 층 침착용 전구체 용액의 기화 및 이송을 위한 방법 및 장치 |
| US8025932B2 (en) * | 2007-02-21 | 2011-09-27 | Colorado School Of Mines | Self-limiting thin film synthesis achieved by pulsed plasma-enhanced chemical vapor deposition |
-
2013
- 2013-09-05 US US14/426,507 patent/US20150211126A1/en not_active Abandoned
- 2013-09-05 KR KR1020157008716A patent/KR20150052283A/ko not_active Application Discontinuation
- 2013-09-05 WO PCT/US2013/058122 patent/WO2014039597A2/en active Application Filing
- 2013-09-06 TW TW102132244A patent/TWI625418B/zh not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200506093A (en) * | 2003-04-21 | 2005-02-16 | Aviza Tech Inc | System and method for forming multi-component films |
| WO2006023501A2 (en) * | 2004-08-16 | 2006-03-02 | Aviza Technology, Inc. | Direct liquid injection system and method for forming multi-component dielectric films |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150052283A (ko) | 2015-05-13 |
| WO2014039597A2 (en) | 2014-03-13 |
| TW201416485A (zh) | 2014-05-01 |
| US20150211126A1 (en) | 2015-07-30 |
| WO2014039597A3 (en) | 2015-07-16 |
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