TWI516630B - 自由基組成化學氣相沉積之原位臭氧硬化之方法 - Google Patents

自由基組成化學氣相沉積之原位臭氧硬化之方法 Download PDF

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TWI516630B
TWI516630B TW099146656A TW99146656A TWI516630B TW I516630 B TWI516630 B TW I516630B TW 099146656 A TW099146656 A TW 099146656A TW 99146656 A TW99146656 A TW 99146656A TW I516630 B TWI516630 B TW I516630B
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substrate
plasma
layer
nitrogen
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王琳琳
美歐里克愛柏亥吉巴蘇
英戈爾尼廷Ｋ
維卡達曼夏可
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應用材料股份有限公司
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Description

自由基組成化學氣相沉積之原位臭氧硬化之方法
本發明大體上有關於製造半導體元件的方法。
【交互參照之相關申請案】
本案主張2010年1月7日申請且發明名稱為「自由基組成化學氣相沉積之原位臭氧硬化方法(IN-SITU OZONE CURE FOR RADICAL-COMPONENT CVD)」之美國臨時申請序號61/293,082案為優先權，全文以引用方式併入本案中以供各方面參考。
自數十年前提出半導體元件起，半導體元件的幾何結構在尺寸上有著戲劇性地縮減。現代半導體製造設備常規性地製造具有45奈米(nm)、32奈米及28奈米之特徵結構尺寸的元件，且即將研發且實施新的設備，以製造具有更小幾何形狀的元件。縮減特徵結構尺寸，導致元件上的結構性特徵具有減小的空間尺寸。元件上的間隙與溝渠寬度狹窄到足以使間隙深度比上間隙寬度的深寬比高到難以用介電材料填滿該間隙。沉積的介電材料容易在完全填滿間隙之前就堵住間隙頂部，而在間隙的中段處產生孔洞或隙縫。
多年來，已研發出許多可避免間隙頂部發生介電材料 堵塞或可「閉合(heal)」已形成之孔洞或隙縫的技術。其中一種已開始採用的方法是使用高流動性前驅物材料，該材料可採液態形式施用於旋轉的基板表面上，例如旋覆玻璃層(SOG)沉積技術。這些流動性前驅物能流入且填充於非常小的基板間隙內，而不會形成孔洞或細小隙縫。然而，一旦這些高流動性材料沉積後，需將之硬化成固體介電材料。
許多情況下，該硬化製程包含加熱處理，以從已沉積的材料中移除碳基及羥基，而留下固體的介電質，例如氧化矽。不幸地，去除碳及羥物種通常會於已硬化的介電質中留下許多孔洞，該些孔洞則降低最終材料的品質。此外，硬化介電質亦易於收縮體積，而可能於介電質與周遭基板的界面處留下裂縫及空隙。在某些情況中，已硬化之介電質的體積可能縮減40%或更多。
因此，需要新的沉積製程及材料，以在已結構化的基板上形成介電材料，又不會在基板的間隙及溝渠內產生孔洞或隙縫或兩者皆產生。亦需要可硬化流動性介電材料且具有較少孔洞及較小體積縮減的方法及材料。在本申請案中係針對這些及其他需求提出方案。
本案描述形成介電層的方法。該些方法包含混合一含矽前驅物及一電漿流之步驟，以及於基板上沉積一含矽 氮層之步驟。藉著在用來沉積該含矽氮層的同一基板處理區域內於含臭氧氛圍中進行硬化，使該含矽氮層轉化成含矽氧層。另一含矽氮層可沉積於該含矽氧層上，以及該些膜層堆疊可於臭氧中再次硬化，且上述所有動作皆無需從該基板處理區域中移除該基板。待完成整數倍的沉積-硬化循環之後，可於含氧環境中在一較高溫度下退火以進行該些含矽氧層之堆疊的轉化。
本發明實施例包括於基板處理腔室內之基板處理區域中的基板上形成一含矽氧層的方法。該些方法包括於基板處理區域中的基板上形成一含矽氮層。形成該含矽氮層的步驟涉及：使含氮氫氣體流入一電漿區域中以產生自由基氮前驅物；於不含電漿的基板處理區域中合併一不含碳的含矽前驅物及該自由基氮前驅物；以及於該基板上沉積一含矽氮層。該些方法更包括於該基板處理區域內的含臭氧氛圍中硬化該含矽氮層。
額外的實施例及特徵係部分描述於以下說明內容中，且部份的額外實施例與特徵則待熟悉該項技術者於檢閱本案說明書或實施本發明時可明瞭或學得。藉由本案說明書中所描述的工具、組合方式及方法可實現及獲得本發明之特徵及優點。
以下描述形成介電層的方法。該些方法包含混合一含 矽前驅物及一電漿流之步驟，以及於基板上沉積一含矽氮層之步驟。藉著在用來沉積該含矽氮層的同一基板處理區域內於含臭氧氛圍中進行硬化，使該含矽氮層轉化成含矽氧層。另一含矽氮層可沉積於該含矽氧層上，以及該些膜層堆疊可於臭氧中再次硬化，且所有動作皆無需從該基板處理區域中移除該基板。待完成整數倍的沉積-硬化循環之後，可於一含氧環境中在一較高溫度下退火以進行該些含矽氧層堆疊的轉化。
某些細節內容的討論可有利地證明，本案請求項的涵蓋範圍不受限於該些可能不完全正確的假設機制。使剛沉積的含矽氮層暴露於臭氧中同時保持相對低的基板溫度所提高的氧含量，勝過僅在含氧環境中於相對高的基板溫度下進行退火所提高的氧含量。這可能是因為藉著混合一自由基氮前驅物與一不含碳之含矽氮前驅物來沉積含矽氮膜會產生相對開放性網狀結構之故。該開放性網狀結構允許臭氧更深入地滲入該膜層中，而使氧化物的轉化作用朝基板方向延伸。於高溫下執行轉化，可封閉靠近表面的網狀結構，因而限制該轉化作用的物理程度。
臭氧的反應性介於氧分子與氧原子之間。氧分子需要較高的溫度以活化氧化作用，而導致靠近表面處的開放性矽氮網狀結構封閉。此種不希望發生的封閉作用限制了該含矽氮層更深部分中的氧化作用。氧原子則太容易於低溫下反應，且同樣會封閉該網狀結構。發現到臭氧 可穩定地滲透深入該開放性網狀結構中，同時不需要高溫來促進氧化作用。現將描述有關形成氧化矽層之方法及系統的更多細節。
根據臭氧理論上取代氫及氮的能力，顯示可能只需要少量加熱或無需加熱便可執行臭氧硬化反應，而能於沉積區域內發生臭氧硬化反應。現將說明有關於使用整合式臭氧硬化反應形成氧化矽之方法與系統的更多細節。
示範性之氧化矽形成製程
第1圖是一流程圖，顯示根據本發明實施例製造氧化矽膜之方法100中的選定步驟。方法100包括提供一不含碳的矽前驅物至一基板處理區域102。該不含碳的矽前驅物可例如是矽氮前驅物、矽氫前驅物或含矽氮氫前驅物、以及其他類型的矽前驅物。該矽前驅物除了不含碳之外，也可不含氧。缺乏氧會導致由該些前驅物所形成之矽氮層中的矽醇基(Si-OH)濃度較低。沉積膜層中的過量矽醇基可在沉積之後從沉積層中移除羥基(-OH)的步驟過程中導致收縮及孔隙度提高。
不含碳之矽前驅物的具體範例可包括矽烷胺類(silyl-amine)，例如H2N(SiH3)、HN(SiH3)2及N(SiH3)3，以及其他矽烷胺類。不同實施例中，矽烷胺的流率(flow rate)可約200sccm或更高、約300sccm或更高，或約500sccm或更高。本文中所提供的所有流率係參照雙腔室式基板處理系統。單晶圓系統可能需要上述流率的一 半量，且其他的晶圓尺寸可能需要根據處理面積而依比例增減流率。這些矽烷胺可與附加氣體混合，該些附加氣體可做為載氣、反應性氣體或同時做為載氣與反應性氣體。該些附加氣體的範例可包括氫氣(H2)、氮氣(N2)、氨(NH3)、氦氣(He)及氬氣(Ar)、以及其他氣體。不含碳之矽前驅物的範例亦可包括單獨含甲矽烷(SiH4)，或含甲矽烷且混合其他含矽氣體(例如N(SiH3)3)、含氫氣體(例如H2)及/或含氮氣體(例如N2、NH3)。不含碳之矽前驅物亦可包括二矽烷、三矽烷，甚至更高階的矽烷類及氯化矽烷類，且該些矽烷類可單獨使用、彼此組合使用或與前述不含碳之矽前驅物組合使用。一般而言，亦可使用含碳的矽前驅物，但需提醒該些膜層可比使用不含碳之矽前驅物時要收縮得更厲害。
自由基氮前驅物亦可供應至該基板處理區域104。該自由基氮前驅物是一種含有氮自由基的前驅物，該含有氮自由基的前驅物是在該基板處理區域外部由較穩定的氮前驅物所生成。例如，可在該處理腔室外部的一腔室電漿區域或一遠端電漿系統(RPS)中活化含有NH3、H2及/或N2的穩定性氮前驅化合物以形成該自由基氮前驅物，隨後輸送該自由基氮前驅物至該基板處理區域內。不同實施例中，該穩定性氮前驅物的流率可約300sccm或更高、約500sccm或更高，或約700sccm或更高。在該腔室電漿區域中產生的該自由基氮前驅物可為‧N、‧NH、‧NH2等類之自由基的其中一者或多者，且 亦可伴有電漿中所形成的已離子化物種。
一般而言，其他自由基前驅物可用以產生含矽氮層。該些自由基前驅物可包含氮或不含氮。若該自由基前驅物中不含氮，將由該含矽前驅物提供氮。在本發明之實施例中，氮可出現在該自由基前驅物及含矽前驅物兩者中。由於具此靈活性，自由基前驅物更常稱為電漿流。同樣地，因為可含氮或不含氮，因此在本文中通常將流入該電漿區域中用以產生電漿流的穩定性氮前驅物稱為穩定氣體。
在採用腔室電漿區域的實施例中，是在該基板處理區域中與一沉積區域分隔開的一區段內產生該自由基氮前驅物，且該些前驅物係在該沉積區域中混合及反應以於一沉積基板上(例如，半導體晶圓)沉積該含矽氮層。該自由基氮前驅物亦可伴有一載氣，例如氫氣(H2)、氮氣(N2)、氦氣，等等。本文中，該基板處理區域在含矽氮層成長過程中以及於低溫臭氧硬化過程中可描述成「不含電漿(plasma-free)。「不含電漿」不必然代表該區域缺乏電漿。腔室電漿區域中的電漿邊界難以界定，且可透過噴淋頭內的孔隙而侵入基板處理區域。在感應耦合電漿的情況中，小量的離子化反應可直接在基板處理區域內作用。再者，可在不消除該形成膜之可流動性質的情況下，於該基板處理區域內產生低強度電漿。於產生自由基氮前驅物的過程中形成離子密度遠低於腔室電漿區域之電漿皆不偏離本文中之用語「不含電漿 (plasma-free)」的範圍。
在該基板處理區域中，不含碳之矽前驅物與自由基氮前驅物混合且反應，以於沉積基板106上沉積一含矽氮膜。可使用實施例中某些製法組合使所沉積的含矽氮膜共形地沉積。其他實施例中，不同於習知氮化矽膜(Si3N4)沉積技術，所沉積的含矽氮膜具有可流動性。形成時的流動性允許該膜流入基板之沉積表面上的狹窄間隙、溝渠及其他結構。一般而言，較高的自由基氮流(radical nitrogen fluxes)產生共形沉積，而較低的自由基流產生產生可流動性沉積。
流動性可能是由混合自由基氮前驅物及不含碳之矽前驅物產生的各種性質所造成。該些性質可包括所沉積之膜中有大量的氫含量及/或存在短鏈的聚矽氮烷聚合物(polysilazane)。於形成該膜期間及形成之後，這些短鏈會成長且形成網狀結構，而產生更緻密的介電材料。例如，所沉積之膜可具有矽烷胺類「Si-NH-Si」的骨架，即是Si-N-H膜。當矽前驅物及自由基氮前驅物兩者均不含碳時，所沉積的含矽氮膜亦實質不含碳。當然，「不含碳(carbon-free)」不必然代表該膜甚至連微量的碳都缺乏。碳污染可能存在於該些前驅物材料中，而尋得途徑進入已沉積的矽氮前驅物中。然而，這些碳雜質的量遠遠少於含碳基之矽前驅物(例如，TEOS、TMDSO，等等)中所含的碳含量。
於該含矽氮層沉積之後，可於含臭氧氛圍中硬化該沉 積基板(步驟108)。沉積後的基板留在用於硬化的同一個基板處理區域中。基板之硬化溫度可約與形成含矽氮膜期間的基板溫度相同，以維持產率。或者，在硬化操作期間，可藉著升高該基板使基板靠近已加熱的面板或噴淋頭而提高溫度。不同實施例中，硬化操作期間的基板溫度可低於120℃、低於100℃、低於90℃、低於80℃或低於70℃。該基板溫度可高於沉積期間的基板溫度，在不同實施例中，可高於50℃、高於60℃、高於70℃或高於80℃。根據所揭露的附加實施例，任一個上述上限可與任一個上述下限組合而形成附加的基板溫度範圍。
該基板處理區域在硬化操作期間可不含電漿，以避免產生相對高濃度的氧原子。氧原子的存在可能過早封閉該含矽氮層的相對開放網狀結構。在實施例中，該基板處理區域中不存在電漿，以避免產生可能封閉靠近表面處之網狀結構且阻礙表面下之氧化作用的氧原子。於硬化步驟期間流入該基板處理區域內的臭氧流率可約200sccm或更高、約300sccm或更高，或約500sccm或更高。硬化步驟期間的臭氧分壓可約10托耳(Torr)或更高、約20托耳或更高，或約40托耳或更高。在某些條件下(例如，基板溫度介於約100℃至約200℃)，發現該轉化作用實質完全，因此實施例中可無需在含氧環境進行相對高溫的退火。
在同一個基板處理區域中執行硬化操作，能實施多次 沉積-硬化循環，並減少每個循環所要求的厚度。此實施例中，該硬化操作僅需轉化一已減少厚度的含矽氮層。如此可減輕對該含臭氧環境的要求、容許較高的氧原子濃度，以及放寬該基板溫度的製程視窗(process window)。一些實施例中，在沉積-硬化循環的硬化期間存在電漿。其他實施例中，該基板處理區域不存在電漿，且該含臭氧環境僅含有小濃度的氧原子。不同實施例中，該含矽氮層於硬化前的膜層厚度可低於1500Å、低於1000Å、低於750Å或低於500Å。在實施例中，結合多次沉積-硬化循環所產生之所有含矽氧層的堆疊厚度可介於400Å至10,000Å間，其主要取決於應用用途。
於步驟109決定是否已達到目標總厚度。若未達目標，接著完成另一次沉積操作(步驟102至106)及另一次硬化操作(步驟108)，且隨後再次將該含矽氧層之厚度與目標厚度作比較。一旦達到目標，基板可留在基板處理腔室中，或從基板處理腔室中移出且傳送至退火腔室以進一步轉化成氧化矽。
完成整數倍的沉積-硬化循環之後，可於含氧氛圍中退火該沉積基板(步驟110)。當引入含氧氛圍時，該沉積基板可留在用於硬化的同一個基板處理區域內，或者該基板可傳送至一引入含氧氛圍的不同腔室中。含氧氛圍可包含一或多種含氧氣體，例如，氧分子(O2)、臭氧(O3)、水蒸氣(H2O)、過氧化氫(H2O2)及氮氧化物(例如NO、NO2，等等)、以及其他含氧氣體。含氧氛圍亦可包含自 由基氧及羥基物種，例如氧原子(O)、氫氧化物(OH)等等，可在遠處產生並輸送至該基板腔室中。亦可存在含氧物種之離子。不同實施例中，基板的氧退火溫度可為約1100℃或更低、約1000℃或更低、約900℃或更低，或約800℃或更低。不同實施例中，基板的溫度可為約500℃或更高、約600℃或更高、約700℃或更高，或約800℃或更高。再一次根據所揭露的附加實施例，任一個上述上限可與任一個上述下限組合而形成附加的基板溫度範圍。
於氧退火期間，該基板處理區域中可存在或不存在電漿。進入CVD腔室的含氧氣體可包含一或多種化合物，該些化合物在進入基板處理區域之前已經活化，例如已自由基化、已離子化，等等。例如，該含氧氣體可包含自由基氧物種、自由基羥基物種等等，該些物種係藉著使較穩定之前驅化合物通過一遠端電漿源或通過利用噴淋頭而與基板處理區域分隔開的腔室電漿區域而活化。該些較穩定之前驅物可包括水蒸氣及過氧化氫(H2O2)，而產生羥基(OH)之自由基與離子，以及該些較穩定之前驅物可包括氧分子及/或臭氧，而產生氧原子(O)之自由基與離子。
硬化及氧退火的含氧氛圍提供氧，以使含矽氮膜轉化成氧化矽膜(SiO2)。如前述，含矽氮膜中缺乏碳，會使最終的氧化矽膜中產生顯著較少的孔洞。亦使該膜在轉化成氧化矽的過程中產生較少的體積縮減(即，收縮)。例 如，由含碳之矽前驅物形成的矽-氮-碳層在轉化成氧化矽時，可收縮40體積%或更多，而實質不含碳的含矽氮膜收縮約15體積%或更少。
現參閱第2圖，另一流程圖顯示根據本發明實施例用以於基板間隙內形成氧化矽膜之方法200中的選定步驟。方法200可包括傳送一含有間隙的基板至一基板處理區域中(步驟202)。該基板可具有多個間隙，用於已形成在基板上之該些元件構件(例如，電晶體)之結構或分隔(spacing)。該些間隙可具有高度及寬度，且其高度比上寬度(即，H/W)所定義的深寬比(AR)顯著大於1：1，例如5：1或更多、6：1或更多、7：1或更多、8：1或更多、9：1或更多、10：1或更多、11：1或更多、12：1或更多，等等。許多情況中，高深寬比是因小的間隙寬度所造成，該間隙寬度的範圍約90奈米至約22奈米或更小，例如約90奈米或更小、65奈米或更小、45奈米或更小、32奈米或更小、28奈米或更小、22奈米或更小、16奈米或更小，等等。
不含碳之矽前驅物與一自由基氮前驅物在該基板處理區域內混合(步驟204)。一可流動的含矽氮層可沉積在該基板上(步驟206)。由於該層可流動，故該層能填入具有高深寬比的間隙中，而不會在填充材料的中心附近產生孔洞或細小隙縫。例如，沉積中的可流動性材料於完全填滿間隙之前，很少會因過早堵塞間隙的頂部而於間隙的中段內留下孔洞。
隨後，可在用以執行步驟204至206之沉積作用的同一個基板處理區域內硬化剛沉積的含矽氮層(步驟208)。在圖示的實施例中，未顯示出多次沉積-硬化循環，但可採用類似於第1圖所描述及顯示的重複方式執行多次沉積-硬化循環。若轉化不完全，可於含氧氛圍中退火該已部分轉化的含矽氧層(步驟210)，以使該含矽氮層轉化成氧化矽。進一步的退火(未顯示)可於惰性環境中在較高的基板溫度下執行，以緻密化該氧化矽層。
於含氧氛圍中硬化及退火該剛沉積的含矽氮層以在該基板(包括基板間隙)上形成氧化矽層(步驟208)。在實施例中，步驟208及210的處理參數係與參照第1圖所述之步驟108及110具有相同範圍。如上述，相較於由含碳前驅物所形成的類似膜層(在熱處理步驟之前該層中存在有顯著量的碳)而言，上述氧化矽層具有較少孔洞及較少體積縮減。許多例子中，體積縮減要夠小(例如，約15體積%或更少)，以避免於在用以填充、修復或消除形成於間隙內之空間的後續熱處理步驟中造成氧化矽收縮。
第3圖是從根據本發明實施例之含矽膜所獲得的傅立葉轉換紅外線光譜(FTIR)。剛沉積的含矽氮膜305顯示在908cm-1至933cm-1附近具有一強峰值，且在835cm-1至860cm-1附近有一強峰值，這顯示存在氫及氮。亦顯示在基板處理區域外部進行臭氧硬化之含矽氮層的FTIR光譜(310)，以及在基板處理區域內部進行臭氧硬化 之含矽氮層的FTIR光譜(315)。在這兩種情況中，與氫相關的峰值皆減小，且其他峰值亦有相符的近似行為。這表示原位硬化的低溫硬化的效果與在專用腔室中進行硬化的效果類似。亦顯示經8次沉積-硬化循環處理之氧化矽的FTIR光譜320，該光譜320顯示該膜中殘留非常少的氫和氮。該多次沉積-硬化循環的相關FTIR光譜還顯示在1100cm-1附近有一個非常強的氧峰值，這表示Si-H-N良好地轉化成氧化矽。
示範性氧化矽沉積系統
可實施本發明實施例的沉積腔室尤其包括高密度電漿化學氣相沉積(HDP-CVD)腔室、電漿增強化學氣相沉積(PECVD)腔室、次大氣壓化學氣相沉積(SACVD)腔室及熱化學氣相沉積腔室、以及其他種類的腔室。可實施本發明實施例之CVD系統的具體範例包括CENTURA ULTIMA® HDP-CVD腔室/系統及PRODUCER® PECVD腔室/系統，可購自美國加州聖大克勞拉市(Santa Clara)的應用材料公司。
能與本發明示例性方法併用的基板處理腔室範例可包括如Lubomirsky等人於2006年5月30日申請發明名稱為「用於介電間隙填充之製程腔室(PROCESS CHAMBER FOR DIELECTRIC GAPFILL)」且共同受讓之美國專利臨時申請案60/803,499號中所顯示及描述的該些腔室，該案全文係以引用方式納入本文中以供各方面 參考。額外的示範系統可包括如美國專利案6,387,207號及6,830,624號中所顯示及描述之該些系統，此兩案亦採引用方式納入本文中以供各方面參考。
沉積系統之實施例可併入用以製造積體電路晶片的更大型製造系統中。第4圖顯示根據所揭露之實施例以沉積腔室、烘烤腔室及硬化腔室所構成的此類系統400。圖中，一對前開式晶圓盒(FOUPs)402提供基板(例如，直徑300毫米之晶圓)，在置入晶圓處理腔室408a至408f其中一者之前，該些晶圓係由機械手臂404接收且放入一低壓保存區406中。第二機械手臂410可用以將基板晶圓從保存區406傳送至該些處理腔室408a至408f，以及將基板晶圓從該些該些處理腔室408a至408f傳回保存區。
該些處理腔室408a至408f可包含一或多個系統構件，用以沉積、退火、硬化及/或蝕刻基板晶圓上的可流動性介電膜。在一種配置中，兩對處理腔室(例如，腔室408c至408d及408e至408f)可用以在基板上沉積可流動性介電材料，以及第三對處理腔室(例如，腔室408a至408b)可用以退火所沉積之介電質。在另一種配置中，同樣的兩對處理腔室(例如，腔室408c至408d及408e至408f)可建構用來沉積及退火基板上的可流動性介電質，而第三對腔室(例如，腔室408a至408b)可用來執行所沉積之膜層的UV或電子束硬化。在又另一種配置中，三對腔室(例如，腔室408a至408f)全設計用以沉積及硬 化該基板上的可流動性介電膜，並且每一個腔室可設置成具有多個升降銷(lift pins)用以升高該基板使之朝向一已加熱噴淋頭，從而升高「整合」硬化步驟(「integrated curing operation」的溫度。在又另一種配置中，兩對處理腔室(例如，腔室408c至408d及408e至408f)可用於該可流動性介電質的沉積與UV或電子束硬化作用，且第三對處理腔室(例如，腔室408a至408b)可用以退火該介電膜。可在與不同實施例所示之製造系統分隔開的腔室中執行任何上述的一或多種製程。
此外，一或多個上述處理腔室408a至408f可建構作為溼式處理腔室。這些處理腔室包括於含有濕氣的氛圍中加熱該可流動性介電膜。因此，系統400的多個實施例可包括溼式處理腔室408a至408b及退火處理腔室408c至408d，以於所沉積的介電膜上執行溼式退火及乾式退火。
第5A圖顯示根據所揭露之實施例的基板處理腔室500。遠端電漿系統(RPS)510可處理一氣體，且該氣體隨後通過一氣體入口組件511。該氣體入口組件511內可看見兩個不同的氣體供應通道。第一通道512攜帶一氣體通過該遠端電漿系統(RPS)510，同時第二通道513則繞過該遠端電漿系統510。在所揭露的實施例中，該第一通道512可供製程氣體使用，該第二通道513則可供處理氣體(treatment gas)使用。且在蓋子(或導電性頂部)521及有孔隔板553之間顯示具有一絕緣環524，該 絕緣環524容許相對於該穿孔隔板553而施加交流(AC)電壓於蓋子521。該製程氣體行經第一通道512而進入腔室電漿區域520，且單獨利用腔室電漿區域520中的電漿或結合使用遠端電漿系統(RPS)510激發該製程氣體。腔室電漿區域520及/或遠端電漿系統510之結合可稱為在本文中的遠端電漿系統。該有孔隔板(亦稱噴淋頭)553將腔室電漿區域520與噴淋頭553下方的基板處理區域570隔開。噴淋頭553容許電漿存在於腔室電漿區域520中，以避免直接激發基板處理區域570中的氣體，同時仍容許已激發的物種從腔室電漿區域520行進至基板處理區域570中。
噴淋頭553設置於腔室電漿區域520與基板處理區域570之間，且容許在腔室電漿區域520內所創造出的電漿流(前驅物或其他氣體的已激發衍生物)通過多個貫穿該板厚度的通孔556。噴淋頭553亦具有一或多個中空體積551，該些體積551可填充蒸汽或氣體形態的前驅物(例如，含矽前驅物)，且可通過多個小孔555而進入基板處理區域570但不直接進入腔室電漿區域520。在此揭露的實施例中，噴淋頭553的厚度大於該些通孔556之最小直徑550的長度。為使從腔室電漿區域520滲入基板處理區域570中的已激發物種維持有效濃度，該些通孔之最小直徑550的長度526可能受限於貫穿噴淋頭553途中所形成之該些通孔556的較大直徑部分。在所揭露的實施例中，該些通孔556之最小直徑550的長度 可能相當於或小於該些通孔556的最小直徑。
在所顯示的實施例中，噴淋頭553可經由該些通孔556分配含氧氣、氫氣及/或氮氣的製程氣體，及/或分配此類製程氣體經腔室電漿區域520中之電漿所激發的電漿流。實施例中，經由第一通道512引入遠端電漿系統510及/或腔室電漿區域520中的製程氣體可包含一或多種下述氣體：氧氣(O2)、臭氧(O3)、氧化亞氮(N2O)、一氧化氮(NO)、二氧化氮(NO2)、氨(NH3)、NxHy(包括N2H4)、甲矽烷、二矽烷、TSA及DSA。製程氣體亦包含一載氣，例如氦氣、氬氣、氮氣(N2)，等等。第二通道513亦可輸送一製程氣體及/或一載氣，及/或膜硬化氣體以用於從正在成長或剛沉積之膜中移除不想要的組成(components)。電漿流可包含製程氣體的已離子化或中性衍生物，且亦在本文中亦可指自由基氧前驅物及/或自由基氮前驅物，該些前驅物係指所引入之製程氣體的原子狀要素。可採電阻方式或使用通過一包埋式通道的熱傳流體直接加熱噴淋頭553，或由腔室電漿區域520中的電漿間接加熱噴淋頭553。不論哪種方式，可於整合式硬化步驟期間藉著升高基板使基板接近該已加熱之噴淋頭553而升高基板溫度，且一旦硬化操作完成，隨後降低基板。
實施例中，該些通孔556的數目可介於約60至約2000個。通孔556可具有各種形狀，但最易製成圓形。所揭露的實施例中，該些通孔556的最小直徑550可介於約 0.5毫米(mm)至約20毫米，或介於約1毫米至約6毫米。亦可自由選擇通孔556的剖面形狀，該剖面形狀可製成錐形、柱形或兩種形狀之組合。不同實施例中，用以引導氣體進入基板處理區域570中的小孔555數目可介於約100至約5000個，或介於約500至約2000個。該些小孔555之直徑可介於約0.1毫米至約2毫米間。
第5B圖是噴淋頭553的底視圖，其用於與根據揭示實施例之處理腔室併用。噴淋頭553對應於第5A圖中所顯示的噴淋頭。該些通孔556繪示成在噴淋頭553底部處具有較大內直徑(ID)且在頂部處具有較小內直徑。小孔555實質平均地分佈在噴淋頭的整個表面上，甚至分佈在該些通孔556之間，以幫助提供更平均的混合。
當通過噴淋頭553中的該些通孔556的電漿流與來自中空體積551且通過該些小孔556之含矽前驅物相混合時，於基板處理區域570中藉由一基座(未顯示)所支撐的基板上產生一示範性膜。雖然可裝備基板處理區域570以承受用於其他製程(例如硬化)的電漿，但在該示範性膜的成長期間不存在電漿。
可在噴淋頭553上方的腔室電漿區域520或噴淋頭553下方的基板處理區域570中點燃電漿。電漿出現在腔室電漿區域520中，以從含氮氫氣體的流入氣流製造出自由基氮前驅物。在該處理腔室之導電性頂部521與噴淋頭553之間施加一典型介於射頻(RF)範圍內的交流(AC)電壓，以於沉積過程中在腔室電漿區域520內點燃電 漿。射頻功率供應器產生13.56MHz的高射頻頻率，但亦可產生單獨的其他頻率，或產生他種頻率與13.56MHz頻率之組合。
當基板處理區域570中的底部電漿啟動以硬化薄膜或清潔圍繞著基板處理區域570的內部表面時，該頂部電漿可能保持低功率或無功率。藉著在噴淋頭553與基座或腔室底部之間施加AC電壓而點燃在基板處理區域570內之電漿。當電漿存在時，可引導清潔氣體進入基板處理區域570內。
基座可具有一熱交換通道，熱交換流體可流經該熱交換通道以控制基板溫度。此種配置容許冷卻或加熱基板溫度以保持相對低溫(約從室溫至約120℃)。熱交換流體可包括乙二醇及水。基座的晶圓支撐盤(較佳為鋁、陶瓷或鋁和陶瓷之組合)亦可使用包埋式單圈加熱器元件採電阻性加熱以達到相對高溫(約120℃至約1100℃)，包埋式單圈加熱器元件係建構成具有兩個完整的平行同心圓狀迴圈。該加熱器元件的外側部分可緊鄰支撐盤的周長而延伸，同時該加熱器元件的內側部分則沿著具有較小半徑之同心圓的路徑延伸。連接至加熱器元件的接線則通過該基座之軸桿(stem)。
利用一系統控制器控制該基板處理系統。一示範性實施例中，該系統控制器包含一硬碟機(hard disk drive)、一軟碟機(floppy disk drive)及一處理器。該處理器包含單板電腦(SBC)、類比及數位輸入/輸出板、介面卡 (interface board)及步進馬達控制器板(stepper motor controller board)。CVD系統的各個部件符合彈性開端式匯流排系統標準(Versa Modular European(VME)standard)，該標準界定各種卡、卡籠及連接器的尺寸及類型。該VME標準亦定義匯流排結構具有一16位元之資料匯流排及一24位元之位址匯流排。
該系統控制器控制CVD機器的所有行動。該系統控制器執行系統控制軟體，該軟體係儲存在電腦可讀媒體中的電腦程式。較佳地，該媒體為硬碟機，但該媒體亦可為他種記憶體。該電腦程式包含多組指令，其指示一特定製程的時序、氣體混合、腔室壓力、腔室溫度、射頻功率大小、基座位置及其他參數。亦可使用儲存於他種記憶裝置(包括如軟碟機或其他適當驅動裝置)中的其他電腦程式對該系統控制器下達命令。
可利用該系統控制器執行一電腦軟體產品，以實施用以在基板上沉積膜層堆疊之製程，或實施用以清潔腔室之製程。能以任何習知的電腦可讀編輯語言撰寫該電腦軟體編碼，例如68000組合語言、C、C++、Pascal、Fortran或其他語言。使用習知文字編輯器將適合的程式編碼輸入於單個或多個檔案中，且儲存或內建於一電腦可用的媒體內，例如該電腦的記憶系統。若已輸入的編碼內容是高階語言，該編碼係經編譯，且所產生的編譯碼隨後與已預編譯之微軟視窗®常式庫的目標碼連結。為了執行該已連結且經編譯的目標碼，系統使用者啟用該目標 碼，使得該電腦系統載入記憶體中的編碼。隨後CPU讀取且執行該編碼以執行程式中確認的工作。
使用者與控制器之間的聯繫係透過平板觸控感應式監視器。在較佳實施例中，使用兩個監視器，一個安裝在清潔室壁中以供操作者使用，另一個安裝在室壁後方以供維修技術員使用。該兩個監視器可同時顯示相同資訊，此種情況下，每次只有一台監視器能接受輸入信息。操作者可觸碰該觸控感應式監視器的一指定區域，以選擇特定的螢幕或功能。所觸碰的區域改變其強調色或顯示新的項目單或螢幕，以確認操作者與觸控感應式監視器之間的通信。除觸控感應監視器之外，亦可額外使用諸如鍵盤、滑鼠或其他指示或通信裝置之其他裝置，或使用上述裝置來取代觸控感應式監視器，以容許使用者與系統控制器溝通。
文中所使用「基板(substrate)」一詞可能是上方具有或不具有膜層的支撐基板。該支撐基板可能是具各種摻雜濃度及摻雜模式(profile)的絕緣體或半導體，且可能例如是用於製造積體電路類型的半導體基板。「氧化矽層」可能包含少量濃度的其他元素組成，例如氮、氫、碳等等。在本發明的一些實施例中，氧化矽在本質上是由矽及氧所構成。處於「已激發狀態」的氣體係指一氣體中至少有一部份的氣體分子處在振動激發、解離及/或離子化狀態。氣體(或前驅物)可能是由兩種或多種氣體(前驅物)所構成之組合物。「溝渠(trench)」一詞用於全文中無疑 是指具有高水平深寬比的已蝕刻幾何結構。從表面上方看來，該些溝渠呈圓形、卵形、多角形、矩形或其他各種形狀。「通孔(via)」一詞係用以代表低深寬比之溝渠，可填充或尚未填充金屬以形成垂直的電性連結。「前驅物(precursor)」一詞係用以代表任何製程氣體或蒸發的液體液滴，其參與反應以移除一表面上的材料或沉積材料於表面上。
數個實施例已說明如上，熟悉該項技術者將理解可在不偏離本發明精神的情況下作出各種修飾、替代構造及等效物。此外，文中未描述許多已知的製程及元件，以避免無謂地混淆本發明。因此，上述內容不應用以限制本發明範圍。
應瞭解，當提出一數值範圍時，除文中另有明確指示，否則介於該範圍之上下限值之間的每個中間值(intervening value，至該下限值單位的十分之一)亦屬明確揭示。介於一所述範圍中的任何所述值或中間值與所述範圍內的任何其他所述值或中間值之間的每個較小範圍亦被涵蓋。這些較小範圍的上下限值可獨立地包含在該範圍內或排除於該範圍之外，且該些含有其中一個限值、不含限值或包含兩限值的各個小範圍亦為本發明所涵蓋，取決於所述範圍中是否有任何特別排除的限值。所述範圍可包含其中一個限值或兩限值均包含在內，且排除任一個限值或兩個限值皆排除的範圍亦為本發明所涵蓋。
除非上下文中另有清楚指示，否則本文及後附申請專利範圍中使用之單數型用語「一」、「一個」及「該」包括複數之意。因此，例如提及「一製程」時，包括多個此類製程；提及「該前驅物」時，包括一或多個前驅物及熟悉該項技術者已知的該些前驅物之等效物，及依此類推。
又，當用於本案說明書及後附申請專利範圍中時，「包括(comprise)」、「包含(comprising)」、「含有(include)」、「具有(including)」及「有(includes)」之用語係意欲載明所述之特徵、整數、組成或步驟的存在，但不排除存在或附加一或多個其他特徵、整數、組成、步驟、動作或基團。
100‧‧‧方法
102、104、106、108、109、110‧‧‧步驟
200‧‧‧方法
202、204、206、208、210‧‧‧步驟
305、310、315、320‧‧‧傅立葉轉換紅外線光譜
400‧‧‧處理系統
402‧‧‧前開式晶圓
404‧‧‧機械手臂
406‧‧‧低壓保持區域
408a、408b、408c、408d、408e、408f‧‧‧處理腔室
410‧‧‧第二機械手臂
500‧‧‧基板處理腔室
510‧‧‧遠端電漿系統
511‧‧‧氣體進入組件
512‧‧‧第一通道
513‧‧‧第二通道
520‧‧‧腔室電漿區
521‧‧‧蓋
524‧‧‧絕緣環
526‧‧‧通孔長度
550‧‧‧通孔之最小直徑
551‧‧‧中空體積
553‧‧‧多孔隔板
555‧‧‧小孔
556‧‧‧通孔
570‧‧‧基板處理區域
參照附圖及本案說明書其餘部份之內容，可進一步瞭解本發明之本質及優點，且於數個附圖中皆使用類似的元件符號來代表相似構件。在某些情況中，元件符號係以連字號連接一次標號，以表示多個相似構件中的其中一個構件。當一元件符號未載明現有的次標號時，則該元件符號係欲代表全體此類的相似元件。
第1圖係一流程圖，顯示根據本發明實施例之用以製造氧化矽膜的選定步驟。
第2圖係另一流程圖，顯示根據本發明實施例之用以 於基板間隙中形成氧化矽膜的選定步驟。
第3圖係一傳立葉轉換紅外線(FTIR)光譜，該光譜係獲自根據本發明實施例之含矽膜。
第4圖顯示根據本發明之實施例的基板處理系統。
第5A圖顯示根據本發明之實施例的基板處理腔室。
第5B圖顯示根據本發明實施例之基板處理腔室的噴淋頭。
100‧‧‧方法
102‧‧‧步驟
104‧‧‧步驟
106‧‧‧步驟
108‧‧‧步驟
109‧‧‧步驟
110‧‧‧步驟

Claims (19)

  1. 一種於一基板處理腔室內之基板處理區域中的一基板上形成一含矽氧層之方法，該方法包括：形成一含矽氮層於該基板處理區域中的該基板上，其中形成該含矽氮層的步驟包括：使一穩定氣體流入一電漿區域，以產生電漿流；於不含電漿的基板處理區域中合併一含矽前驅物與該電漿流，其中該含矽前驅物係不含碳；及沉積一含矽氮層於該基板上；以及於該基板處理區域內的一含臭氧氛圍中硬化該含矽氮層，以形成該含矽氧層。
  2. 如申請專利範圍第1項所述之方法，更包括於該基板處理區域內的該基板上形成一第二含矽氮層，其中形成該第二含矽氮層之步驟包括：使該穩定氣體流入該電漿區域，以產生電漿流；於該基板處理區域中合併一含矽前驅物與該電漿流；及沉積該第二含矽氮層於該基板處理區域內的該基板上；以及於該基板處理區域內的一含臭氧氛圍中硬化該第二含矽氮層。
  3. 如申請專利範圍第1項所述之方法，其中該基板處理 區域在形成該含矽氮層的操作期間係不含電漿，以避免該含矽前驅物的直接電漿激發作用。
  4. 如申請專利範圍第1項所述之方法，其中該基板處理區域在硬化該含矽氮層的操作期間係不含電漿。
  5. 如申請專利範圍第1項所述之方法，其中該基板溫度於該硬化操作期間係高於沉積該含矽氮層之操作期間，但不高於超過50℃。
  6. 如申請專利範圍第1項所述之方法，其中在沉積該含矽氮層之操作期間的一基板溫度係低於100℃。
  7. 如申請專利範圍第1項所述之方法，其中在該硬化操作期間的一基板溫度係低於200℃。
  8. 如申請專利範圍第1項所述之方法，其中該含矽氮層之厚度小於1500Å或約1500Å。
  9. 如申請專利範圍第1項所述之方法，其中該基板被升高並朝向一已加熱之噴淋頭，以於該硬化操作期間加熱該基板。
  10. 如申請專利範圍第1項所述之方法，其中該穩定氣 體係一含氮氫氣體，且該電漿流包括一自由基氮前驅物。
  11. 如申請專利範圍第10項所述之方法，其中該含氮氫氣體包括氨。
  12. 如申請專利範圍第1項所述之方法，其中該含矽前驅物包括一含矽氮前驅物。
  13. 如申請專利範圍第1項所述之方法，其中該含矽前驅物包括N(SiH3)3。
  14. 如申請專利範圍第1項所述之方法，其中該含矽氮層包括一不含碳的Si-N-H層。
  15. 如申請專利範圍第1項所述之方法，更包括在硬化操作之後，於一含氧氛圍中升高該基板的溫度至高於600℃或約600℃的一氧退火溫度。
  16. 如申請專利範圍第15項所述之方法，其中該含氧氛圍包含選自下列所組成之群組中的一或多個氣體：氧原子、臭氧及水蒸汽(H2O)。
  17. 如申請專利範圍第1項所述之方法，其中該基板經 圖案化且具有一間隙，該間隙之寬度約45奈米或更小，以及其中形成於該間隙內的該氧化矽層係實質無孔。
  18. 如申請專利範圍第1項所述之方法，其中該電漿區域是位於一遠端電漿系統中。
  19. 如申請專利範圍第1項所述之方法，其中該電漿區域係該基板處理腔室的一分隔區域，藉由一噴淋頭而與該無電漿基板處理區分隔開。
TW099146656A 2010-01-07 2010-12-29 自由基組成化學氣相沉積之原位臭氧硬化之方法 TWI516630B (zh)

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US20120003840A1 (en) 2012-01-05
JP2013516788A (ja) 2013-05-13
SG182333A1 (en) 2012-08-30
WO2011084752A2 (en) 2011-07-14
KR20120125623A (ko) 2012-11-16
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TW201134975A (en) 2011-10-16
WO2011084752A3 (en) 2011-10-27

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