TW201133624A - Stress management for tensile films - Google Patents

Stress management for tensile films Download PDF

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Publication number
TW201133624A
TW201133624A TW099135111A TW99135111A TW201133624A TW 201133624 A TW201133624 A TW 201133624A TW 099135111 A TW099135111 A TW 099135111A TW 99135111 A TW99135111 A TW 99135111A TW 201133624 A TW201133624 A TW 201133624A
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Taiwan
Prior art keywords
substrate
layer
precursor
ruthenium
plasma
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TW099135111A
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English (en)
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Jing-Mei Liang
Anjana M Patel
Nitin K Ingle
Shankar Venkataraman
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Applied Materials Inc
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Publication of TW201133624A publication Critical patent/TW201133624A/zh

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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Description

201133624 六、發明說明： 【交互參照之相關申請案】 本發明係關於在西元2009年8月6曰提出申請且發明 名稱為「FORMATION OF SILICON OXIDE USING NON-CARBON FLOWABLE CVD PROCESSES」之臨時專 利申請案號61/23 1，729，其在此以引置方式併入本文作 為參考》 【發明所屬之技術領域】 本發明係關於伸張膜之應力管理。 【先前技術】 Α #幾何形 自從數十年前引進了半導體元件，半導髏A# 4^5·備常規地 態之尺寸已經顯著地減小。現代半導體製透 製造具有250 nm、1 80 nm與65 nm特徵尺<
，而在間隙 元件，炎 且正在發展且1 之元件。減小έ 小的空間尺寸 中間隙深度對f 有挑戰性以介1 電材料堵塞間 係傾向於在間隙完全被填滿之前於頂部堵蹇 中間產生了空隙或縫隙。
S 數年來，已經發展許多技術來避免使介電 4 201133624 隙的頂部’或「密封」已經形成的空隙或縫隙。一種方 式係已經以高可流動的前驅物材料來開始，高可流動前 驅物材料是在液相中應用到旋轉的基材表面（例如S〇G 沉積技術）。這些可流動的前驅物可流動到非常小的基材 間隙内且將其填滿’而不會形成空隙或弱的縫隙。然而， 一旦這些高可流動的材料被沉積了，其需要被固化且被 硬化成固體介電質材料。 在許多例子中，硬化製程係包括一熱處理以從所沉積 材料移除碳與輕基團而留下諸如氧化石夕之固體介電質。 不幸地，移除之碳與羥物種時常在硬化之介電質中留下 孔隙，其會降低最終材料的品質。此外，硬化之介電質
的體積可減少40%或更多。 因此，存在有新沉積製程與材料的需求，其可在結構 化基材上形成介電質材料而不會在基材間隙與溝槽中產 生空隙、缝隙或兩者。亦存在有材料與方法的盆
縮以及容納仍發生的收縮。 求。 【發明内容】 本發明描述了一 具有低破裂傾向之間隙填充氧化矽層 5 201133624 的形成。沉積係涉及—可& 了⑽動含矽層之形成，其中該可 流動含矽層係促進溝桿的植 、 再價的填充。在高基材溫度下的後續 處理係造成比根據習知JL ig . 爆$知技藝方法所形成可流動膜更少之 介電質膜中破裂。+ 相迎在形成間隙填充氧化矽層前所沉 積之一可壓縮襯裡居， 層且可堡縮襯裡層降低了後續沉積 之膜會破裂的傾向。在可續叙人Μ ^ 任了机動含矽層後之一可壓縮覆蓋 層亦已經被確定可減少破裂。可單獨地或組合地利用可 壓縮襯裡層與可壓縮覆蓋層來減少且時常消除破裂。此 外，在所揭不實施例中，已經確定可壓縮覆蓋層可使得 氮化矽之下置層被轉變成氧化矽層。 在一貫施例中’一種形成一氧化;g夕層於一基材上之方 法，該基材含有一溝槽，該方法包含以下步驟：傳送該 基材到一基材處理腔室内；形成一可壓縮襯裡層於該基 材上且在該溝槽中；形成一介電質層於該基材上且在該 溝槽中，其中該介電質層係起初可流動的；及固化該介 電質層。 在又另一實施例中，一種形成一氧化發層於一基材上 之方法，該基材含有一溝槽，該方法包含以下步驟：傳 送該基材到一基材處理腔室中之一基材處理區域内；使 一電漿前驅物流動到一遠端電漿區域内，以形成電漿流 出物；在該基材處理區域中結合該些電漿流出物和一含 矽前驅物之流動，其中該含矽前驅物之流動尚未由一電 漿所激發；形成一含矽與氧層於該基材上且在該溝槽 中；形成一可壓縮覆蓋層於該含石夕與氧層上方；及固化 Μ 6 201133624 該含梦與氧層。 在又另一實施例中’ 一種形成一氧化石夕層於一基材上 之方法’該基材含有一溝槽’該方法包含以下步驟：傳 送該基材到一基材處理腔室中之一基材處理區域内；使 一電漿前驅物流動到一遠端電襞區域内，以形成電漿流 出物；在該基材處理區域中結合該些電漿流出物和一含 石夕前驅物之流動’其中該含矽前驅物之流動尚未由一電 聚所激發；形成一含矽與氮層於該基材上且在該溝槽 中；形成一可壓縮覆蓋層於該含矽與氮層上方；及在一 含氧氛圍中加熱該基材，以將該不含碳之含矽與氮層轉 變成該氧化矽層。 額外之實施例與特徵係部分地揭示在以下說明中，且 其。卩分地對於熟習此技藝之人士在參閱說明書時變得明 顯或可藉由實施所揭示之實施例而瞭解。所揭示之實施 例之特徵與優點可藉由描述在說明書中之裝置、組合和 方法來瞭解和獲得。 【實施方式】 本發月私述了一具有低破裂傾向之間隙填充氧化石夕層 :形成。沉積係涉及-可流動含矽層之形成，其中該可 流動含矽層係促進溝槽的填充。在高基材溫度下的後續 處理係造成比根據習知技藝方法所形成可流動膜更少之 質膜中破裂。描述在形成間隙填充氧化梦層前所沉 s 201133624 積之一可壓縮襯裡層，且可壓縮襯裡層降低了後續沉積 之臈會破裂的傾向。在可流動含矽層後之一可壓縮覆蓋 層亦已經被確定可減少破裂。可單獨地或組合地利用可 壓縮襯裡層與可壓縮覆蓋層來減少破裂。此外，在所揭 示實施例中，已經確定可壓縮覆蓋層可使得氮化矽之下 置層被轉變成氧化矽層。 不欲限制申請專利範圍的範疇到假設的製程機構，包 括—可壓縮襯裡層與（或）一可壓縮覆蓋層係被認為在後 、、只處理的期間或之後能夠穩定化可流動間隙填充氧化矽 層。可流動膜可能需要固化作為一有所區別的固化步驟 或作為一在後續處理期間加熱膜堆疊（包括間隙填充膜） 之自然副產物。典型地，間隙填充臈是經由去氣（〇ut㈣ 來減少質量且發展伸張應力。這樣的一層在此可稱為一 伸張層。可壓縮襯裡層係被認為在以可流動間隙填充氧 化矽層來填充間隙前可穩定化溝槽。可壓縮襯裡層與（或） 可壓縮覆蓋層的存在亦可實體地黏附到且敎化間隙填 充層。基材之實體彎曲度，整體而言，亦可藉由可壓縮 層的存在而減輕’其中該可壓縮層係減少了在固化間隙 填充膜期間造成的彎曲且減少了在後續處理期間其伸張 應力。現將描述關於形成氧化矽層之方法與系統的額外 細節。 示範性氧化矽形成製程 第1圖為-流程圖，其顯示根據本發明實施例之製造 氧化石夕膜之方法1〇〇中經選擇之步驟。方法削包括藉 201133624 由在基材上之高密度電漿CVD(HDp_cVD)來沉積一氧化 石夕襯裡層102。HDP-CVD {形成氧化石夕層之一示範性方 法，其中該氧化矽層係展現伸張應力（特別是在複合沉積 製程後一旦冷卻基材時）。可使用其他方法（例如 PECVD、LP-CVD、或烘爐氧化物）來形成氧化矽可壓縮 襯？里層，其對於在固化/加熱所完成膜堆疊之期間與之後 抑制膜堆疊中之裂缝形成也是同樣有效的。可壓縮襯裡 層亦可以是藉由各種技術（包括HDP-CVD、PECVD、 LP-CVD)與藉由使用高溫烘爐來生長之氮化矽。 方法100更包括提供一不含碳之矽前驅物到反應腔室 104。不含碳之矽前驅物可以是，除了其他類型之矽前驅 物以外，例如一矽與氮之前驅物、一矽與氫之前驅物、 或含碎氣與風之前驅物。這些前驅物之特定實例可包 括矽烷胺，諸如 H2N(SiH3)、HN(SiH3)2 與 N(SiH3)3 等。 這些矽烷胺可和額外的氣體混合’該些額外的氣體係作 為载氣、反應性氣體、或兩者。這些額外的氣體的實例 可包括％、A、NH3、He與Ar等。不含碳之矽前驅物 的貫例亦可包括矽燒（SiH4) ’獨立地或和其他含石夕氣體 (例如N(SiH3)3)、含氫氣體（例如Ha)、與（或）含氮氣體（例 如N2、NH3)混合。 亦可提供一自由基氮前驅物到反應腔室1〇6。自由基 氮前驅物包含藉由激發電漿中之含氮前驅物所產生的電 聚流出物’並且示範性含氮前驅物可包括N2〇、NO、 N〇2、NH4〇H、NH3、與N2。自由基氮前驅物可以是在 9 201133624 反應腔室外從更穩定之氮前驅物所產生之含氮自由基物 種。舉例而言，一穩定之氮前驅物化合物（諸如上述所列 示者）可在反應腔室外之一電漿單元中被活化以形成自 由基氮前驅物，其接著被傳送到反應腔室内。所產生的 自由基氮前驅物可包括·Ν、·ΝΗ、.NH2等之一或多者， 並且亦可由形成在電聚中的離子化物種來伴隨。 在反應腔室中’未激發之不含碳之矽前驅物與自由基 氮前驅物係混合且反應，以在沉積基材（其具有溝槽形成 在其表面上）上沉積一含矽與氮之膜1〇8。藉由習知技藝 間隙填充技術（諸如HDP-CVD)使用較不可流動膜來填充 溝槽而不形成空隙或縫隙可能是困難的。溝槽可具有高 度與寬度而定義了高度對寬度（即H/w)之深寬比（AR)， 其係顯著地大於1:1(例如5:1或更大、6:1或更大、7:ι 或更大、8:1或更大、9:1或更大、1〇:1或更大、11:1或 更大12.1或更大等）。在許多例子中，高AR是由於約 0 nm至約22 nm或更小（例如約咖、65 nm、45謂' 32⑽、22 nm、16 nm等）的小間隙寬度。 不像傳統的I化石夕（813乂）膜，經沉積之含妙與氮膜具 有可机動特徵’可流動特徵容許其可流動到基材之沉積 面上之窄間隙溝槽與其他結構内。由於層是可流動 ::其可填充具有高深寬比之間隙，而不會在填充材料 的周圍產生空隙或縫隙。舉例而言，一沉積可流動 料較不可能在㈣完全地被填滿前預成熟地堵塞間隙 頂部。這有助於減少或消除維持在間隙中間的空隙。 10 201133624 可流動性可以是至少部分地由於經沉積之膜中的顯著 氫成分。舉例而言，經沉積之膜可具有矽氮烷類型之 Si-NH-Si骨幹（即Si-N-H膜）。可流動性亦可導因自矽氮 烷類型之短鍊聚合物。當矽前驅物與自由基氮前驅物不 含碳時’經沉積之含矽與氮膜亦為實質上不含碳的。當 然，「不含碳」不必然意謂著膜缺乏甚至少量的碳。碳污 染物可存在於前驅物材料中，其找到其進入經沉積之含 矽與氮膜的途徑。然而，這些碳雜質的量是比在具有碳 份額之矽前驅物（例如TEOS、TMDSO等）中所發現的少 多了。 在沉積了含矽與氮層後’沉積基材可被引進到一含氧 氛圍110«當引進含氧氛圍時，沉積基材可保持在反應 腔室中；或者，基材可被傳送到引進有含氧氛圍之不同 腔至。含氧氛圍可包括一或多種含氧氣體，諸如分子氧 (〇2)、臭氧（〇3)、水蒸氣（h2〇)、與氧化氮（NO、N〇2等）， 除了其他含氧氣體以外。含氧氛圍亦可包括自由基氧與 經基物種’諸如原子氧（〇)、氫氧化物（〇H)等，其可遠端 地被產生且被傳送到基材腔室内。含氧物種之離子亦可 存在。 含氧氛圍係提供氧以將含矽與氮膜轉變成氧化矽 (Si〇2)膜11〇。如前所述，在含矽與氮膜中缺乏碳係顯著 地造成最終氧化矽臈中所形成之更少孔隙。從沉積到退 火之淨收縮是藉由沉積一可流動含石夕與氮臈且將其轉變 成氧化梦（相較於起初地沉積一可流動含梦與氧膜）來減 201133624 少。在轉變製程期間，基材溫度可以為約25<t至約11〇〇 °C (例如約 200。(：、約 30(TC、約 40(TC、約 5〇〇。〇、約 6〇〇 °C、約 70(TC、約 80(TC、約 90(TC、約 1〇〇(rc 等）。在 許多情況中’體積減少是稍微足以（例如約15 v〇1 %或更 小）避免後熱處理步驟來填充、治癒或消除因收縮的氧化 矽而形成在間隙中的空間❶在一實施例中，轉變可發生 成兩部分。此兩部分轉變可包括一低溫臭氧固化以起始 氧化’接著在含氧環境中進行一高溫退火。 第1圖之製程描述了一製程，其中氧化矽是藉由先沉 積一含矽氮層且接著將此層轉變成氧化矽來形成。在其 他實施例中，經沉積之膜是藉由自由基氧前驅物以及尚 未由電漿激發之含碳前驅物來產生。然後，經沉積之膜 將為一含矽與氧膜，其在後續處理期間（相較於涉及含矽 與氮膜之製程）可能經歷更多收縮。沒通過電漿之示範性 含碳前驅物可包括TM0S、TriM〇S、TEOS、OMCTS、 HMDS、TMCTR、TMCTS、OMTS、TMS、HMDSO、與（或）、 TMDSO。自由基氧前驅物包含藉由激發電漿中之含氧前 驅物所產生的電衆流出並且示範性含氧前驅物可包 括 〇2、03、N2〇、N0、N〇2、h2〇2、h2〇、與 nh4〇H。 乂此方式>儿積之膜中的破裂亦可藉由使用在此描述之可 壓縮襯裡層與覆蓋層來減少。 實施例可包括多個具有不同溫度與氛圍之加熱階段。 舉例而δ，可在較低第一溫度且在包括蒸氣（HA)之氛圍 中執仃第一加熱階段，可在較高第二溫度且在實質上
12 S 201133624 缺乏水蒸氣之乾的含氧氛圍中執行一第二加熱階段。亦 可在一含非氧氛圍（例如乾N2、He、Ar等）中執行一第三 加熱階段。 現參照第2圖’顯示了另-流程圖，其係繪示根據本 發明實施例之在溝槽中形成氧化矽膜之方法2〇〇中經選 擇之步驟。方法200可包括傳送-具有表面溝槽之基材 到一基材處理區域内。溝槽可用以指定形成在基材上之 元件部件（例如電晶體）之間隔與結構。方法2〇〇包括提 供一不含碳之矽前驅物到反應腔室202。不含碳之妙前 驅物係關連於第1圖被討論。一自由基氮前驅物被提供 到反應腔室204，如參照第i圖所描述者。再次地，替 代性實施例係涉及引進一未激發之含碳前驅物與一自由 基氧前驅物，以形成一可流動含矽與氧膜，其中該可流 動含矽與氧膜在後續處理期間會呈現更多的收縮。 不含碳之矽前驅物與自由基氮前驅物係混合且反應以 在沉積基材上沉積一可流動含矽與氮膜（操作2〇6)。膜之 可流動本質係促進表面溝槽之填充，其中使用以習知技 藝間隙填充技術（諸如HDP-CVD)來製造之較不可流動膜 疋難以完全地填滿該些溝槽》在沉積後，臭氧流動到反 應區域内且基材被加熱到相當低的溫度，以起始氧化且 將含矽與氮膜轉變成二氧化矽（操作2〇7)。 接著’ 一可壓縮覆蓋層被沉積在經固化之膜上方，其 中該經固化之膜含有矽、氧與可能的氮208。一種沉積 在可壓縮應變下覆蓋層的方式是以HDP-CVD來沉積， 13 201133624 類似沉積第1圖之襯裡層的方法。可使得覆蓋層比襯裡 層更厚’這是因為溝槽在製程中係在此點大量地被填 充。可壓縮覆蓋層被整合到製程流程中，並且由於可壓 縮覆盍層所提供的額外材料，可致使更薄可流動膜的使 用。在一些實施例中，溝槽沒有被間隙填充層完全地填 滿’在此情況中’可壓縮覆蓋層係填充一些溝槽體積。 再次地’可使用其他方法（例如PECVD、LP-CVD、烘爐 氧化物）來製造可壓縮覆蓋層’其對於在退火膜堆疊的期 間與之後抑制所完成膜中裂縫形成是同樣有效的。可壓 縮覆蓋層亦可以是藉由各種技術（包括HDP-CVD、 PECVD、LP-CVD)與藉由使用高溫烘爐來生長之氮化矽。 在沉積了可壓縮覆蓋層後’沉積基材被引進到一含氧 氛圍中210。再次地，沉積基材可維持在引進有含氧氛 圍之反應腔室中；或者，基材可被傳送到引進有含氧氛 圍之不同腔室。含氧氛圍係如參照第i圖來描述。含氧 氖圍長:供氧以完成將含石夕與氮膜轉變成氧化石夕之轉變， 其中該轉變是在固化期間起始。吾等已經發現儘管存在 有可壓縮覆蓋層，轉變會進行。在含氧氛圍中加熱經固 化之含矽與氮層再次地在基材上與在基材間隙中形成氧 化矽層。相較於在熱處理步驟前以含碳前驅物形成之類 似層（其在層中具有顯著量的碳），氧化矽層具有更少的 孔隙與更少的體積減少。在所揭示實施例中，可結合第 1圖之可壓縮襯裡層與第2圖之可壓縮覆蓋層，以進一 步保護膜堆疊免於發展裂縫。 201133624 第3圖為另一流程圖，其係繪示根據本發明實施例之 製造氧化矽膜之額外示範性方法300中經選擇之步驟。 方法300包括藉由高密度電漿CVD(HDP-CVD)在基材上 沉積一氧化矽襯裡層 302。可使用其他方法（例如 PECVD、LP-CVD、與烘爐氧化物）來形成可壓縮襯裡層， 只要此替代性方法形成一可壓縮襯裡層可有助於在處理 順序中之固化與加熱步驟的期間與之後減少裂縫。方法 300更包括引進一含矽前驅物與一自由基氧前驅物到基 材處理區域内304。 自由基氧前驅物可在電漿CVD沉積腔室外從例如穩 定之含氧氣體（例如分子氧（〇2)、臭氧（〇3)、水蒸氣、過 氧化氫（H202)、與氧化氮（例如N20、N02等））來產生。 如同第1 -2圖之方法，亦可使用穩定氣體之混合物來形 成自由基物種。自由基氧亦可被產生在反應腔室之一分 離區塊中，其中反應腔室之該分離區塊係和基材處理區 域分隔。在此分離區塊中，穩定之含氧氣體由遠離基材 處理區域之電漿來激發。分隔物可具有穿孔且在此可稱 為噴頭。 在所揭示實施例中，含矽前驅物係直接地被引進到基 材處理區域内以避免電漿激發。含矽前驅物可包括有機 矽烷化合物，包括 TMOS、TriMOS、TEOS、OMCTS、 HMDS、TMCTR、TMCTS、OMTS、TMS、與 TMDSO。 含矽前驅物亦可包括不具有碳之矽化合物，諸如矽烷、 二矽烷等。若經沉積之氧化物膜為一摻雜氧化物膜，亦
S 15 201133624 可使用摻質前驅物（TEB、ΤΜΒ、；Β2ΐί6、ΤΈΡΟ、PU3、Ρ2ΐί6 與ΤΜΡ，除了其他硼與磷摻質以外）。摻質亦可用在第 1-2圖所討論的方法中。 在反應腔室中，矽前驅物與自由基氮前驅物係混合且 反應，以在沉積基材（其在其表面中形成有溝槽）上沉積 一含矽與氧之膜306。溝槽可具有高度與寬度而定義了 高度對寬度（即H/W)之深寬比（AR)，其係顯著地大於 1:1(例如5:1或更大、6:1或更大' 7:1或更大、8:1或更 大、9:1或更大、ΐ(Μ或更大、1ηι或更大、12:1或更 大等）。在許多例子中’高AR是由於約9〇 nm至約22 nm 或更小（例如約 90 nm、65 urn、45 nm、32 nm、22 nm、 16 nm等）的小間隙寬度。 以這些方法所製造之膜係起初可流動的，這使得其能 流動到基材之沉積表面上之窄間隙或溝槽與其他結構 内。膜流動到具有高深寬比之間隙内，而不會在填充材 料中心的周圍產生空隙或弱縫隙。舉例而言，一沉積可 流動材料較不可能在間隙完全地被填滿前預成熟地堵塞 間隙之頂部而在間隙中間留下空隙。 在沉積了含矽與氧膜後，一可壓縮覆蓋層被沉積在含 矽與氧膜上方308。一種沉積在可壓縮應變下覆蓋層的 方式是以HDP_CVD來沉積，類似沉積第i圖之襯裡層 與第2圖之覆蓋層的方法。可使得覆蓋層比第i圖與操 作302之襯裡層更厚’這是因為溝槽在製程中係在此點 大量地被填充。可壓縮覆蓋層被整合到製程流程中，並 16 £ 201133624 且由於可壓縮覆蓋層所提供的額外材料，可致使更薄可 流動膜的使用。在替代性實施例中，使用襯裡層而 用覆蓋層’並且使用覆蓋層而不使用襯裡層。 在操作3 10 ’膜堆疊被固化以移除一些殘留在膜中的 流動試劑。儘管存在有可壓縮覆蓋層，任何從固化膜之 去氣（outgas)會發生。固化步驟可以不是必要的，取決於 期望之最終膜堆疊的性質。在其他實施例中，膜是在進 一步處理（其無可避免地涉及了一些基材加熱）的過程中 被固化。 現討論在此呈現之可壓縮層的一般性質，根據所揭示 實施例之可壓縮襯裡層係比溝槽寬度之一半更薄，以為 了容許後續沉積之可流動膜能夠流動到剩餘的間隙内。 在不同實施例中’襯裡層之厚度可小於或約4〇〇a、小於 或約300A、小於或約200人、或小於或約ι5〇Αβ可壓縮 襯裡層必須厚到足以對溝槽提供必要的穩定性，並且在 不同實施例中，其厚度可大於或約25A、大於或約50A、 大於或約100A、大於或約150人。任何上限可和任何下 限結合以形成額外之實施例。 在此呈現之可壓縮覆蓋層具有比可壓縮襯裡層更大的 自由度’這是因為其不會受到基材溝槽之寬度所限制。 在不同實施例中，可壓縮覆蓋層之厚度可大於或約 25A、大於或約5〇A、大於或約1〇〇A、大於或約2〇〇A、. 大於或約300A、或大於或約400A。典型地，可壓縮覆 蓋層之厚度之上限是由涉及可流動層之最終厚度的特定 λ 17 201133624 製程流程來決定。 iiDP-CVD是可用以形成在此所描述之可壓縮襯裡與 可壓縮覆蓋層之一種方法。在HDP-CVD沉積期間，基 材可位在和用來沉積可流動層之腔室不同的腔室中。一 不範性沉積腔室是可從美國加州聖大克勞拉市之應用材 料公司獲得的Ultima HDP腔室。當處理300 mm晶圓之 基材時’基材在沉積可壓縮膜期間可被維持在低於約5〇〇 C或約300 C至約400°C，並且所施加之總源電漿rf功 率可以是5000 W至1〇,〇〇〇 W(排除偏功率卜基材偏功率 可以是2000 W至7000 W。更高之偏功率係和襯裡與覆 蓋層中更高之可壓縮應力有關。可使用除了 Ultima HDP 以外的腔室，其具有操作條件的轉換，該轉換係可從處 理工具供應業者獲得或可僅為熟習此技藝之人士所熟 知。非偏RF功率產生器所放射之頻率可以為約2 MHz， 並且偏RF功率產生器所放射之頻率可以為約ι3 % MHz。在HDP-CVD期間，各種含氧與含矽源可流動到處 理區域内，並且典型的前驅物包括〇2與SiH4。在使用此 兩前驅物的情況中，〇2: SiH4之流速比例可以為約〇 25.1 至約1:1。 在沉積含矽膜（其在上述實例中包括氮與（或）碳）的期 間，可流動膜生長會進行’同時基材溫度被維持在相當 低的溫度。在沉積期間’可流動氧化物膜可在低溫下被 >儿積在基材表面上，其中該低溫是藉由冷卻基材來維 持。基座可包括位在基座轴内之加熱與（或）冷卻導管， 18 £ 201133624 其在不同實施例中可將基座與基材之溫度設定在約4(rc 至約200 C、約l〇〇c至約16(TC、小於約1〇〇。〇、或小 於約40°C。 在可流動膜之生長期間，腔室電漿區域或基材處理區 域中之壓力可小於或約100 T〇rr、小於或約5〇 τ〇π、小 於或約20 T〇rr、小於或約1〇 T〇rr、小於或約5 T〇rr。在 不同實施例中，在任一區域或兩區域中之壓力可大於或 約0.25 Ton*、大於或約〇· 5 T〇rr、大於或約J T〇rr、大 於或約2T〇rr、大於或約5T〇rr。根據所揭示實施例，各 下限可和壓力之各上限結合以形成額外之適當壓力範 圍。 在可流動膜之生長期間（以為了製造自由基氧與（或）自 由基氮前驅物）’腔室電漿區域中之電漿條件在不同實施 例中可包括約3000 W至約15,〇〇〇 w、約400 W至約 1〇,〇〇0 W、或約5000 W至約8000 W之rf功率。 示範性基材處理系統 沉積系統之實施例可被併入到更大之製造系統以製造 積體電路晶片。第4圖顯示根據所揭示實施例之沉積、 烘烤與固化腔室的一這樣系統4〇〇。在此圖中，一對前 開式整合艙（FOUPs)402供應基材（例如300 mm直徑晶 圓）’該些基材由機械手臂404接收且在被放置到基材處 理腔室408a-f之一者前被放置到一低壓固持區域4〇6 内。一第二機械手臂410可用來從固持區域406傳送基 材晶圓到處理腔室408a-f且返回。
19 S 201133624 處腔至4〇8a-f可包括用以沉積、退火、固化與（或） 蚀刻基材晶圓上之可流動介電質膜的—或多個系統部 件。在一組•態中，㈣處理腔室（例如408C-d與408e-f) 可用、積可流動介電質材料在基材上，並且第三對處 理腔室（例如4G8a-b)可用以退火經沉積之介電f。在另 一組態甲，此相同之兩對處理腔室（例如4〇8c d與4〇8e f) 可又、冗積且退火基材上之可流動介電質膜，而第三對 處理腔室（例*彻a姻用於經沉積之膜的w或電子 束固化在又另一組態中，所有三對處理腔室（例如⑽h_f) 可設以沉積、固化可流動介電質膜在基材上。在再另 ”且I中兩對處理腔室（例如408c-d與408e-f)可均用於 可流動；丨電質之沉積以及uv或電子束固化，而第三對 處理腔室（例如408a_b)可用以退火介電質膜。可瞭解， 用於可机動介電質膜之沉積、退火與固化腔室的額外組 態可由系统400設想出。 此外，處理腔室4〇8a_f之一或多者可設置成一濕處理 至這'^處理腔至包括在包括濕氣之氛圍中加熱可流 I電質膜。因此，系統4〇〇之實施例可包括濕處理腔 室408a-b與退火處理腔室4〇8c d，以對經沉積之介電質 媒執行濕與乾退火。 第5A圖為根據所揭示實施例之一基材處理腔室5〇〇。 遠端電槳系統（remote plasma system; RPS)5 10可處理 氣體’該氣體接著行經一氣體入口組件511〇氣體入 口組件511内可看見兩個分離的氣體供應通道。第一通
20 S 201133624 道512係承載通過RPS 510之氣體，而第二通道513係 繞過RP S 5 1 〇。在所揭示之實施例中，第一通道5 12可 用於一製程氣體，並且第二通道513可用於一處理氣 體。蓋（或導電頂部）521與穿孔分隔物553係顯示在其之 間具有一絕緣環524，絕緣環524容許AC電位相對於穿 孔分隔物553被施加到蓋521。製程氣體行經第一通道 512到腔室電漿區域520内，並且可獨立地由腔室電漿 區域520中之電漿或和RPS 510之組合來激發。腔室電 漿區域520與（或）RPS 510之組合在此可稱為一遠端電漿 系統。穿孔分隔物（亦稱為喷頭）553係將腔室電漿區域 520與喷頭553下方之基材處理區域570分離。喷頭553 容許電漿存在於腔室電漿區域520中以避免直接地激發 基材處理區域570中的氣體，同時仍容許經激發之物種 可從腔室電漿區域520行進到基材處理區域570内。 喷頭553位在腔室電漿區域520與基材處理區域57〇 之間，並且容許腔室電漿區域520中建立的電漿流出物 (前驅物或其他氣體之激發衍生物）通過複數個橫跨板厚 度之穿孔556。喷頭553亦具有一或多個中空容室551， 該些中空容室551可被填充以蒸氣或氣體形式的前驅物 (諸如含石夕刖驅物）且其通過小孔555到基材處理區域570 内但不直接到腔室電漿區域520内。在此揭示之實施例 中，喷頭553比穿孔556之最小直徑之長度更厚。為了 維持激發物種從腔室電漿區域520穿過到基材處理區域 570之顯著集中’穿孔之最小直徑55〇之長度526可藉
21 S 201133624 5 53之較大直徑部分來限制。 孔556之最小直徑550之長度 由形成穿孔556通過噴頭 在所揭示之實施例中，穿 可和穿孔556之最小直徑具有相同大小等級。 在所顯示之實施例中，一旦藉由腔室電漿區域52〇中 之電漿所激發，喷頭553可散佈（經由穿孔556)含有氧、 氫與（或）氮之製程氣體與（或）這樣製程氣體之電漿流出 物。在實施例中’經由第一通道512引進到Rps5i〇與（或） 腔室電漿區域520之製程氣體可含有氧（〇2)、臭氧⑴ο、 仏〇、齡、>1〇2、丽3、队1^(包括_4)、石夕燒、二矽烷、 TSA、與DSA之一或多者。製程氣體亦可包括一载氣， 諸如氦、氬、氮（NO等。第二通道513亦可輸送一製程 氣體與（或）一載氣、與（或）一用以從生長或所沉積之臈移 除不希望之成分的膜固化氣體。電漿流出物可包括製程 氣體之離子化或中性衍生物，並且在此亦可稱為一自由 基氧前驅物與（或）一自由基氮前驅物（其參照所引進之製 程氣體的原子構成物 在實施例中，穿孔556之數量可為約6〇個至約2_ 個。穿孔556可具有各種形狀，但為最容易製造的圓形。 在所揭示之實施例中，穿孔556之最小直徑55〇可為約 〇.1 mm至約20_或約！ mm至約6mm。亦存在有選 擇穿孔之截面形狀的自由，其可以是圓錐形、圓柱形、 或此兩形狀之組合。在不同實施例中，用以將氣體引進 到基材處理區域別内之小孔555之數量可為約⑽個 至約5000個或約5〇〇個至約2000個。小：〜 J札555之直徑 22 1 201133624 可為約0.1 mm至約2 mm。 第5 B圖為根據所揭示實施例和處理腔室併同使用之 喷頭553的仰視圖。喷頭553係和第5A圖顯示的喷頭相 應。穿孔556係被繪示成在喷頭553之底部具有—較大 内k(ID)且在頂部具有__較小内徑（ID)。小孔奶係實質 上均勻地散佈在喷頭表面，甚至在該些穿孔5%之間， 其有助於提供比在此所描述之其他實施例更均勻的混 合。 田通過喷頭553之穿孔5S6而抵達之電漿流出物和通 過J孔555(其源自中空容室55丨）而抵達之含矽前驅物結 合時，一不範性膜被建立在基材處理區域57〇中由基座 (未示出）所支標之基材上。儘管基材處理區域可設 以支援用於其他製程（諸如固化）之電漿，該示範性膜之 生長期間不存在有電漿。 可在喷頭553上方之腔室電漿區域52〇中或噴頭553 下方之基材處理區域57〇中引發一電漿。典型地，在沉 積期間’射頻（RF)範圍中之AC電壓係被施加在處理腔 室之導電頂部521與喷頭553之間，以在腔室電漿區域 520中引發一電漿。當基材處理區域570中之底電漿被 啟動以固化一膜或清潔基材處理區域570之内表面時， 頂電漿被被保持在低或沒有功率。基材處理區域570中 之電漿是藉由施加AC電壓於喷頭553與腔室之基座或 底部來引發。當電聚存在時，可將一清潔氣體引進到基 材處理區域570内。 23 201133624
基材處理系統由-系統控制器來控制。在-示範性實 施例令’系統控制器包括—硬碟機、一軟碟機與一處理 器。處理盗含有單板電腦⑷响-一 computer; SB 類比與數位輸入/輸出板、界面板、與步進馬達控制器 VD系統之各部件係符合Versa ⑹寧⑽ (VME)標準’其定義了板、卡籠（咖deage)、與連接器尺 寸和類型。VME標準也將匯流排結構義成16位元資 料匯流排與24位元位址匯流排。 系:統控制器係控制CVD機台之所有活動、系統控制器 執行系”先控制軟體，其中該系統控制軟體是儲存在一電 腦可哨媒體中的電腦程式。較佳地’媒體是硬碟機，但 媒體亦可以是其他類型的記憶體。電腦程式包括指令 組’其可命令特定製程之時間點、氣體混合、腔室壓力、 腔室溫度、RF功率位準、载座位置、與其他參數。儲存 在其他記憶體裝置（包括例如軟碟或其他適當的裝置）上 之其他電腦程式亦可用以指示系統控制器。 可使用由系統控制器執行之電腦程式產品來實現一種 用以在基材上沉積一膜堆疊之製程或一種用以清潔一腔 至之製程《電腦程式碼能夠以任何傳統之電腦可讀程式 化語言來撰寫：例如，68000組合語言、c、C++、Pascal
Fortran、或其他者。適當的程式碼係使用傳統的文字編 輯器被轉成單一檔案或多個檔案，並且被儲存或内嵌在 一電腦可用媒體（諸如電腦之記憶體系統）中。若轉換之 碼文字是屬於高階語言，碼被編譯，並且最終的編譯器 24 201133624 碼接著連結到預編譯之微軟資料庫常規之目的碼。為了 執行連結之編譯之目的碼，系統使用者係援引目的碼， 使電腦系統將記憶體中之碼載入。然後，cpu讀取且執 行該碼’以實施程式中所指定的任務。 使用者與控制器之間的界面是經由—平面面板碰觸敏 感性螢幕。在使用兩個螢幕之較佳實施例中，一螢幕是 裝設在清潔室壁中以供操作者使用，而另一螢幕是裝設 在壁後面以供維護技師使用。此兩螢幕可同時地顯示相 同的資訊，在任一情況中僅一螢幕會在一時間點接收輸 入。為了選擇特定之顯示幕或功能，操作者係碰觸該碰 觸敏感性螢幕之一指定區域。經碰觸的區域會改變其凸 顯顏色，或一新選單或顯示幕會被顯示，確認了操作者 與碰觸敏感性螢幕之間的溝通。可使用其他裝置（諸如鍵 盤、滑鼠、或其他指向或溝通裝置）來取代或添加到該碰 觸敏感性螢幕，以容許使用者和系統控制器溝通。 在此使用之「基材」可以是一具有或不具有層形成在 其上的支撐基材。支撐基材可以是一絕緣體或一具有各 種摻雜濃度和輪廓之半導體，並且可以是例如用來製造 積體電路之類型的半導體基材。在此使用之處於「激發 狀態」之氣體係描述一氣體，其中至少一些氣體分子是 處於震動地激發、解離與（或）離子化狀態。一氣體可以 疋兩種或更多種氣體的組合。術語溝槽是在說明書中用 來不意指經蝕刻之幾何形態必然具有大的水平深寬比。 從表面上方觀之，溝槽可以是圓形、橢圓形、多邊形、
25 S 201133624 矩形、或各種其他形狀。 已經描述了一些實施例，熟習此技藝之人士可瞭解的 是，在不脫離本發明之精神下，可使用各種潤飾、替代 性結構與均等物。此外，沒有描述許多已知的製程與構 件，以為了避免不必要地模糊化本發明。因此，上述說 明不應被視為會限制本發明之範轉。 當提供數值之範圍時，應瞭解，亦特定地揭示了該範 圍之上限與下限間的各中間數值（達下限單位的十=之 一，除非文中清楚地指明）。介於任何所載明數值或所載 明範圍内之中間數值與任何其他所载明數值或在該所載 明數值内之中間數值之間的各更小範圍係被涵蓋。這些 更小範圍之上限與下限可獨立地被包括在該範圍内或被 排除該範圍外，並且包括有任一限制、沒有包括限制、 或兩者之各範圍亦被涵蓋在本發明中。所載明範圍包括 限制之一I或兩纟_，排除該些所包括之限制#任一者 或兩者的範圍亦被包括。 如在此所使用者且如隨附申請專利範圍中所示，單數 形式「一」、「一個」與「該」係包括複數個參照物，除 非文中清楚地指明。因此，例如，「一製程」係包括 個這樣的製程，並且「該前驅物」係包括熟習此技藝之 人士所熟知之-或多個前驅物及其均等物，及諸如此類 者。 此外，在說明書中和隨时請專利範圍中使用之術語 包含」與「包括」係意圖指明所記載特徵、整數、部 26 a 201133624 件或步驟的存在，但其不會排除一或多個其他特徵、 人、整 數、部件、步驟、動作或群組的存在或添加。 【圖式簡單說明】 可藉由參照說明書和圖式之剩餘部分來進一步瞭解本 發明之本質和優點，其中圖式裡使用類似的元件代表符 號來指稱類似的元件。在一些情況中，一次標係關連到 一元件代表符號且跟隨在一連字號後，以表示多個類似 元件之一者。當參照一元件代表符號而沒有指定一次桿 時’吾等係欲意指所有這樣的多個類似元件。 第1圖為一流程圖，其繪示根據所揭示實施例之製造 一多層氧化矽膜之經選擇的步驟。 第2圖為另一流程圖，其繪示根據所揭示實施例之形 成一多層氧化矽膜之經選擇的步驟。 第3圖為另一流程圖，其繪示根據所揭示實施例之形 成一多層氧化矽膜之經選擇的步驟。 第4圖顯示根據所揭示實施例之基材處理系統。 第5八®顯示根據所揭示實施例之基材處理系統。 第5B圖顯示根據所揭示實施例之基材處理系統之嘴 頭。 【主要元件符號說明】 100 方法
27 S 201133624 102- 110 處理步驟 200 方法 202-210 處理步驟 300 方法 302-3 10 處理步驟 400 沉積系統 402 FOUP 404 機械手臂 406 固持區域 408 處理腔室 410 第二機械手臂 500 基材處理腔室 510 RPS 511 氣體入口組件 512 第一通道 513 第二通道 520 腔室電漿區域 521 蓋 524 絕緣環 526 最小直徑之長 550 最小直徑 55 1 中空容室 553 噴頭 555 小孔 28 201133624 556 穿孔 570 基材處理區域 29

Claims (1)

  1. 201133624 七、申請專利範圍： 1. 一種形成一氧化矽層於一基材上之方法，該基材含有 一溝槽，該方法包含以下步驟： 傳送該基材到一基材處理腔室内； 形成一可壓縮襯裡層於該基材上且在該溝槽中； 形成一介電質層於該基材上且在該溝槽中，其中 該介電質層係起初可流動的；及 固化該介電質層。 2·如申請專利範圍第1項所述之方法，其中該可壓縮襯 裡層是使用烘爐、PECVD、LP-CVD與HDP-CVD之 一者來沉積。 3. 如申§青專利範圍第1項所述之方法，更包含以下步驟： 在固化該介電質層前，形成一可壓縮覆蓋層於該 介電質層上方。 4. 如申請專利範圍第1項所述之方法，其中該溝槽之寬 度為約5 0 n in或更小。 5. —種形成一氧化矽層於一基材上之方法，該基材含有 一溝槽，該方法包含以下步驟： 傳送該基材到一基材處理腔室中之一基材處理 30 S 201133624 區域内； 使一電漿前驅物流動到一遠端電漿區域内，以形 成電漿流出物； 在該基材處理區域中結合該些電漿流出物和一 含矽前驅物之流動，其中該含矽前驅物之流動尚未由 一電漿所激發； 形成一含矽與氧層於該基材上且在該溝槽中； 形成一可壓縮覆蓋層於該含矽與氧層上方；及 固化該含矽與氧層。 6. 如申請專利範圍第5項所述之方法，更包含以下步驟： 在形成該含矽與氧層於該基材上前，形成一可壓 縮襯裡層。 7. 如申請專利範圍第5項所述之方法，其中該含矽前驅 物包含一含矽與碳前驅物，並且該些電漿流出物包含 一自由基氧前驅物。 8. 如申請專利範圍第7項所述之方法，其中該含矽與碳 前驅物包含 TMOS、TriMOS、TEOS、OMCTS、HMDS、 TMCTR、TMCTS、OMTS、TMS、HMDSO 與 TMDSO 之至少一者，並且該電漿前驅物包含〇2、〇3、N20、 NO、N02、H2〇2、H2◦與 NH4OH 之至少一者。 31 201133624 9.如申請專利範圍第5項所述之方法，其中該溝槽之寬 度為約50 nm或更小。 10. 如申請專利範圍第5項所述之方法，其中該含矽前驅 物包含一含矽與氮前驅物，該些電漿流出物包含—自 由基氮前驅物’並且該方法更包含以下步驟： 在一含臭氧氛圍中加熱該基材，以至少部分地將 一經沉積之膜轉變成該含矽與氧層。 11. 如申請專利範圍第5項所述之方法，其中該含矽與氮 前驅物包含H2N(SiH3)、HN(SiH3)2與N(SiH3)3之至少 者’並且該電漿前驅物包含nh3、nh4oh、n2o、 NO、N〇2、N2與H2之至少一者。 12. 如申請專利範圍第5項所述之方法，其中該遠端電聚 區域是位在該基材處理腔室内且藉由一喷頭和該基 材處理腔室分離。 之方法，其中該可壓縮 LP-CVD 與 HDP-CVD 覆 之 13.如申請專利範圍第5項所述 蓋層是使用烘爐、PECVD、 一者來沉積。 方法，該基材含有 14. 一種形成一氧化矽層於一基材上之 一溝槽，該方法包含以下步驟： 32 S 201133624 傳送該基材到一基材處理腔室中之一基材處理 區域内； 使一電漿前驅物流動到一遠端電漿區域内，以形 成電漿流出物； 在該基材處理區域中結合該些電漿流出物和一 含石夕前驅物之流動’其中該含矽前驅物之流動尚未由 一電漿所激發； 形成一含矽與氮層於該基材上且在該溝槽中； 形成一可壓縮覆蓋層於該含矽與氮層上方；及 在一含氧氛圍中加熱該基材，以將該不含碳之含 矽與氮層轉變成該氧化矽層。 15. 如申請專利範圍第14項所述之方法，更包含以下步 驟： 在形成該含珍與氮1層於該基材上前，形成一可壓 縮襯裡層。 16. 如申請專利範圍第14項所述之方法，更包含以下步 驟： 在形成該可壓縮覆蓋層前，在一含臭氧氛圍中固 化該含梦與氮層。 17. 如申請專利範圍第14項所述之方法，其中該含矽前 驅物包含一含矽與氮前驅物’並且該些電漿流出物包 33 201133624 含一自由基氣前驅物。 18. 如申請專利範圍第17項所述之方法， 氮前驅物包含H2N(SiH3)、HN(SiH3)2與 少一者，並且該電聚前驅物包含N2〇 NH4OH、NH3、n2 與 h2 之至少一者。 19. 如申請專利範圍第14項所述之方法， 圍包含〇2、〇3與H2〇之至少一者。 20. 如申請專利範圍第14項所述之方法， 寬度為約50 nm或更小。 21·如申請專利範圍第14項所述之方法， 漿區域是位在該基材處理腔室内且藉 基材處理腔室分離。 22.如申請專利範圍第14項所述之方法， 覆蓋層是使用烘爐、PECVD、LP-cvo 之一者來沉積》 其中該含矽與 N(SiH3)3 之至 、NO、N02、 其中該含氧氛 其中該溝槽之 其中該遠端電 由一喷頭和該 其中該可壓縮 與 HDP-CVD 34
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WO2011049800A2 (en) 2011-04-28
JP2013508975A (ja) 2013-03-07
US20110034035A1 (en) 2011-02-10
KR20120091235A (ko) 2012-08-17
WO2011049800A3 (en) 2011-07-14
CN102598228A (zh) 2012-07-18

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