TW201308432A - 降低釋氣的覆蓋層 - Google Patents

降低釋氣的覆蓋層 Download PDF

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TW201308432A
TW201308432A TW101118985A TW101118985A TW201308432A TW 201308432 A TW201308432 A TW 201308432A TW 101118985 A TW101118985 A TW 101118985A TW 101118985 A TW101118985 A TW 101118985A TW 201308432 A TW201308432 A TW 201308432A
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precursor
layer
ruthenium
nitrogen
plasma
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lin-lin Wang
Abhijit Basu Mallick
Nitin K Ingle
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Applied Materials Inc
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Abstract

在此描述一種形成氧化矽層的方法。該方法首先藉由自由基成分的化學氣相沉積(CVD)沉積含矽氮與氫(聚矽氮烷)膜。該含矽氮與氫膜是藉由將自由基前驅物(在遠端電漿中激發)結合無激發且無碳的矽前驅物而形成。覆蓋層形成為覆於該含矽氮與氫膜上，而避免轉變成氧化矽之前底下的膜性質隨時間發展。該覆蓋層是藉由將自由基氧前驅物(在遠端電漿中激發)與無激發的含矽與碳前驅物結合而形成。該等膜藉由暴露至含氧環境而轉變成氧化矽。該兩種膜可在相同的基材處理腔室中沉積且可不破真空地沉積。

Description

降低釋氣的覆蓋層 【相關申請案之交互參照】
此申請案主張美國臨時申請案61/492,914之權益，該申請案由Wang等人於2011年6月3日提出，發明名稱為「CAPPING LAYER FOR REDUCED OUTGASSING」，該申請案以全文形式在此併入，以供所有目的之用。
此發明關於半導體處理技術。
自從數十年前導入半導體元件以來，半導體元件的幾何形狀在尺寸上已劇烈減少。現代的半導體製造設備例行生產具有45 nm、32 nm與28 nm之特徵尺寸的元件，且正開發及實施新設備以製作具有更小的幾何形狀的元件。減少的特徵尺寸造成元件上的結構性特徵結構具有減少的空間尺度。元件上的間隙與溝槽之寬度變窄至間隙深度對間隙寬度的深寬比高得足以造成難以用介電材料填充該間隙的地步。在間隙完全填充前，沉積的介電材料易於在頂部阻塞，在間隙中間產生空隙或縫線(seam)。
過去幾年，已開發許多技術去避免使介電材料阻塞間隙頂部或「癒合」已經形成的空隙或縫線。已以高度可 流動的前驅物材料開始進行一項解決手段，可以液相施加該高度可流動的前驅物材料至旋轉基材表面(例如，SOG沉積技術)。這些可流動的前驅物能夠流進非常小的基材間隙並且填充該等間隙，而不形成空隙或脆弱縫線。然而，一旦這些高度可流動的材料沉積，該等高度可流動的材料必須被硬化成固體介電材料。
許多例子中，該硬化步驟包括熱處理，以從沉積的材料移除碳與氫氧基，而留下諸如氧化矽的固體介電質。不幸的是，離開的碳與氫氧物種經常在硬化的介電質中留下孔隙，這些孔隙降低最終材料之品質。此外，硬化的介電質也傾向在體積上縐縮，此現象可於介電質與周圍基材的介面處留下裂隙與空間。一些例子中，硬化的介電質的體積可減少40%或更多。
旋塗介電質(SOD)也已用於流入圖案化基材上的特徵結構。該材料大體上由矽氮烷類型的膜轉變成氧化矽，該矽氮烷類型的膜含有矽、氮與氫。含有矽、氮與氫的膜一般在高溫下於含氧環境中轉變成氧化矽。來自環境的氧替換氮與氫以建立氧化矽膜。對某些電路構造而言，對氧環境的高溫暴露可能摧毀底下的膜。此考量導致需要在製造流程期間維持在「熱預算」內。熱預算的考量已大幅限制SOD至結合底下的氮化矽層的流程，該氮化矽層能夠保護底下的特徵結構免受氧化(例如DRAM應用)。
已開發替代性方法，該等替代性方法藉由自由基成分 的CVD沉積含矽氮烷層。自由基成分的CVD可藉由激發一種前驅物並且將該前驅物與無激發的含矽前驅物在無電漿的基材處理區域中結合而建立可流動膜。膜性質(包括密度)可能在時間中會稍微改變，直到含矽氮烷膜轉變成氧化矽為止。控制膜性質的發展(evolve)改善使用這些膜的元件的製造能力。因此，需要新的沉積製程與材料以形成不會隨時間發展的介電材料。此需要與其他需要在本發明中獲得解決。
在此描述一種形成氧化矽層的方法。該方法首先藉由自由基成分的化學氣相沉積(CVD)沉積含矽氮與氫(聚矽氮烷)膜。該含矽氮與氫膜是藉由將自由基前驅物(在遠端電漿中激發)結合無激發且無碳的矽前驅物而形成。覆蓋層形成為覆於該含矽氮與氫膜上，而避免轉變成氧化矽之前底下的膜性質隨時間發展。該覆蓋層是藉由將自由基氧前驅物(在遠端電漿中激發)與無激發的含矽與碳前驅物結合而形成。該等膜藉由暴露至含氧環境而轉變成氧化矽。該兩種膜可在相同的基材處理腔室中沉積且可不破真空地沉積。
本發明的實施例包括在基材上形成氧化矽層的方法。該等方法包括以下步驟：形成包含矽、氮與氫的第一層，該步驟藉由以下步驟完成：將無激發的前驅物流進遠端 電漿區域以產生自由基前驅物，在無電漿的基材處理區域中將無碳的含矽前驅物結合該自由基前驅物，及沉積無碳的含矽氮與氫層覆於該基材上。該等方法進一步包括以下步驟：形成包含矽與碳的第二層，該步驟藉由以下步驟完成：將無激發的含氧前驅物流進遠端電漿區域以產生自由基氧前驅物，將含矽與碳前驅物與自由基氧前驅物在無電漿的基材處理區域中結合，及沉積含矽氧與碳的覆蓋層覆於該含矽氮與氫層上。
額外的實施例與特徵部分在隨後的實施方式中提出，而部分對於熟習此技術者而言，在詳閱本說明書後可清楚該等實施例與特徵，或者可由操作所揭示的實施例而學得。可藉由本說明書中所述的設備、各式組合物及方法而明瞭及獲得所揭示的實施例之特徵與優點。
在此描述一種形成氧化矽層的方法。該方法首先藉由自由基成分的化學氣相沉積(CVD)沉積含矽氮與氫(聚矽氮烷)膜。該含矽氮與氫膜是藉由將自由基前驅物(在遠端電漿中激發)結合無激發且無碳的矽前驅物而形成。覆蓋層形成為覆於該含矽氮與氫膜上，而避免在轉變成氧化矽之前底下的膜性質隨時間發展。該覆蓋層是藉由將自由基氧前驅物(在遠端電漿中激發)與無激發的含矽與碳前驅物結合而形成。該等膜藉由暴露至含氧 環境而轉變成氧化矽。該兩種膜可在相同的基材處理腔室中沉積且可不破真空地沉積。
已發現以自由基成分的CVD含矽氧與碳膜覆蓋自由基成分的CVD含矽氮與氫膜降低及/或消除一旦將基材暴露空氣後隨時間釋氣及伴隨的膜性質的發展。沒有含矽氧與碳覆蓋層，膜的性質與化學當量可能隨著時間改變。這些膜在時間上發展，這是由於含矽物種、氨氣與類似物的釋氣所致。該等性質也可能發展，這是由於吸收存在於一般製造設施內的周圍大氣(空氣)中的水或其他成分所致。改變膜性質可能會因需要嚴密控制膜形成與另一基材處理系統或腔室內的處理之間的延遲，而使製造製程複雜化。這些複雜與需求都是不被期望的。已發現此述的含矽氧與碳覆蓋層抑制釋氣，但仍容許底下的含矽氮與氫膜轉變成含矽與氧膜且轉變成氧化矽。
已發現根據在此所含的方法以含矽氧與碳膜覆蓋自由基成分的CVD膜在基材暴露至一般清潔室大氣時顯現不會發展之性質。現在，將描述關於形成氧化矽層的方法與系統的額外細節。
示範性氧化矽形成製程
第1圖是流程圖，圖示根據本發明之實施例製作氧化矽膜的方法100中所選步驟。方法100包括以下步驟：提供無碳的含矽前驅物至基材處理區域102。實施例中，該無碳的含矽前驅物不通過電漿激發，所以該前驅物原 封不動地行進至基材處理區域中。隨後僅藉由即將要描述的自由基前驅物提供激發。該無碳的含矽前驅物除了其他類的矽前驅物外特別可以是例如含矽與氮前驅物、含矽與氫前驅物或含矽氮與氫前驅物。缺乏碳減少了沉積膜的縐縮。含矽前驅物除了無碳之外可為無氧。缺乏氧造成由前驅物形成的含矽與氮層中有低濃度的矽烷醇(Si-OH)基。沉積膜中過剩的矽烷醇基團(moiety)可能在從沉積層移除氫氧(-OH)基團的後沉積步驟期間引發孔隙度與縐縮增加。
無碳的矽前驅物之特定範例可包括矽烷胺，除了其他矽烷胺之外，特別可以諸如為H2N(SiH3)、HN(SiH3)2與N(SiH3)3。不同實施例中，矽烷胺的流速可為約200 sccm或更大、300 sccm或更大或者約500 sccm或更大。在此所給的所有流速是參考雙腔室基材處理系統。單一晶圓系統將需要這些流速的一半，而其他晶圓形狀/尺寸將需要經過以處理面積縮放(scaled)的流速。這些矽烷胺可與額外氣體混合，這些額外氣體可作為載氣、反應性氣體或前述二者。額外氣體排除其他氣體之外可特別包括H2、N2、NH3、He、Ne及/或Ar。無碳的含矽前驅物之範例也可包括甲矽烷(SiH4)，該甲矽烷可單獨存在或與其他含矽氣體(例如N(SiH3)3)、含氫氣體(例如H2)及/或含氮氣體(例如N2、NH3)混合。無碳的含矽前驅物也可包括乙矽烷、丙矽烷、更高等級的矽烷與氯化矽烷，前述矽烷為單獨存在或彼此結合或與先前提及的無 碳含矽前驅物結合。
也提供自由基前驅物至基材處理區域104。自由基前驅物描述在基材處理區域外的電漿激發中由任何穩定物種(惰性或反應性)產生的電漿流出物。該自由基前驅物可以是含氮自由基前驅物，該含氮自由基前驅物在此是指自由基氮前驅物。該自由基氮前驅物是一種在基材處理區域外由較穩定的氮前驅物所生成的含氮自由基前驅物。在此穩定的前驅物可指無激發的前驅物，以指示該前驅物尚未通過電漿。可在腔室電漿區域或另一遠端電漿系統(RPS)中活化含有NH3、聯胺(N2H4)及/或N2的穩定的氮前驅物化合物以形成該自由基氮前驅物，該自由基氮前驅物隨後被輸送進入基材處理區域，以激發無碳的含矽前驅物，前述的遠端電漿系統(RPS)是位在處理腔室外。將穩定氮前驅物活化成自由基氮前驅物涉及解離，該解離可特別藉由除其他方法之外的以下方法完成：熱解離、紫外光解離及/或電漿解離。電漿解離可涉及：在遠端電漿生成腔室中由氦、氬、氫(H2)、氙、氨(NH3)等點燃電漿，及將穩定的氮前驅物導入電漿區域以生成自由基氮前驅物
不同實施例中，穩定的氮前驅物也可以是包含NH3與N2、NH3與H2、NH3與N2與H2及N2與H2的混合物。也可使用聯胺以取代NH3或與NH3結合，且可用於涉及N2與H2的混合物中。不同實施例中，穩定的氮前驅物之流速可為約300 sccm或更大、約500 sccm或更大或者 是約700 sccm或更大。在腔室電漿區域中產生的自由基氮前驅物可以是．N、．NH、．NH2等之一或多者，且可伴隨在電漿中形成的離子化物種。在本發明的實施例中，氧源也可在遠端電漿中與較穩定的氮前驅物結合。添加氧源預先使膜載有氧，同時減少了流動性。氧源可包括O2、H2O、O3、H2O2、N2O、NO或NO2之一或多者。
在運用腔室電漿區域的實施例中，自由基氮前驅物在基材處理區域的區段中生成，該區段與沉積區域分隔，在該沉積區域，該等前驅物混合並且反應而沉積含矽與氮層於沉積基材上(例如半導體晶圓)。自由基氮前驅物亦可伴隨諸如氫(H2)、氮(N2)、氦、氖、氬等載氣。在此可將基材處理區域描述為在生長含矽氮與氫層期間及後續製程期間為「無電漿」。「無電漿」並非必然指該區域缺乏電漿。腔室電漿區域中電漿的邊界是難以界定的，且可能經由噴頭中的穿孔(aperture)侵入基材處理區域上。在感應耦合電漿的情況中，例如可直接在基材處理區域內啟動少量的離子化。再者，低強度的電漿可在基材處理區域中建立，而不至於消除形成的膜的可流動之本質。在建立自由基氮前驅物期間離子密度遠低於腔室電漿區域的電漿的所有成因不偏離在此所用的「無電漿」之範疇。
在基材處理區域中，無碳的矽前驅物與自由基氮前驅物混合並且反應，而在沉積基材上沉積含矽氮與氫膜106。實施例中，以某些配方組合，所沉積的含矽氮與氫 膜可共形地沉積。其他實施例中，所沉積的含矽氮與氫膜具有可流動特性，此可流動特性與習知氮化矽(Si3N4)膜沉積技術並不類似。形成期間可流動的本質使膜得以在固化前流進狹窄的特徵結構中。在本發明的實施例中，基材溫度可介於約0℃與約225℃之間、約室溫(25℃)與約125℃之間，或介於約40℃與約95℃之間。在實施例中，這些溫度範圍也應用至即將描述的覆蓋層。
含矽氮與氫膜中的氮可源自自由基前驅物或無激發的前驅物之任一者(或源自於前述二者)。一些實施例中，該無碳的含矽前驅物可基本上無氮。然而，其他實施例中，無碳的含矽前驅物與自由基氮前驅物二者皆含有氮。在第三套實施例中，自由基前驅物可基本上無氮而用於含矽氮與氫層的氮可由無碳的含矽前驅物供應。所以，在此自由基前驅物可指「自由基氮及/或氫前驅物」，意味該前驅物含有氮及/或氫。可以此類推，流進電漿區域而形成自由氮及/或氫前驅物的前驅物可指含氮及/或氫前驅物。此命名法則可應用到在此揭示的每一實施例。在實施例中，含氮及/或氫前驅物包含氫(H2)，而自由基氮及/或氫前驅物包含．H等。
回到圖示於第1圖的特定範例，含矽氮與氫膜的可流動性可能是由於從將自由基氮前驅物與無碳的含矽前驅物混合造成的各種性質。這些性質可包括在沉積的膜中有顯著的氫成分及/或存在短鍊的聚矽氮烷聚合物。在形成膜期間或之後，這些短鍊生長並且互成網絡，而形成 更加緻密的介電材料。例如沉積膜可具有矽氮烷形式的Si-NH-Si骨架，即無碳的Si-N-H膜。當含矽前驅物與自由基前驅物二者皆無碳時，沉積的含矽氮與氫膜也實質上無碳。當然，「無碳」並非必然意味該膜缺乏甚至痕量的碳。碳混入物(contamination)可存在於前驅物材料中而找到進入沉積的含矽與氮前驅物的途徑。然而，這些碳雜質的量遠低於具有碳基團的矽前驅物(例如正矽酸乙酯(tetraethylorthosilicate)、四甲基二矽氧烷(tetramethyldisiloxane))中可見的量。
該製程中的此點，在本發明的實施例中，製程流出物可由基材處理區域移除。製程流出物可包括任何未反應的無碳的含矽前驅物、未反應的自由基氮前驅物、惰性的載氣及來自膜生長的反應副產物。在所揭示的實施例中，可藉由將惰性物種流進基材處理區域及/或經由排放通口排放而替換製程流出物。沉積覆蓋層前，基材可不暴露至空氣，以進一步將膜性質的發展降到最低。
方法100也包括在沉積區域外的遠端電漿系統(RPS)中遠端生成自由基氧前驅物108。該自由基氧前驅物包括在RPS中建立的電漿流出物且可含有原子氧。在實施例中，與用於在操作104中建立自由基氮前驅物的相同RPS可用於建立操作108的自由基氧前驅物。自由基氧前驅物可藉由將含氧前驅物解離而生成，該含氧前驅物諸如分子氧(O2)、臭氧(O3)、氮氧化合物(例如NO、NO2、N2O等)、氫氧化合物(例如H2O、H2O2等)、碳 氧化合物(例如CO、CO2等)及其他含氧前驅物與多種前驅物之組合。解離含氧前驅物以生成自由基氧前驅物可藉由用於在操作104建立自由基氮前驅物相同的手段完成。
自由基氧前驅物隨後被導入沉積腔室108，在該處它可第一次與含矽與碳前驅物混合，該含矽與碳前驅物也被導至腔室110。自由基氧前驅物與矽前驅物(與其他可存在於反應腔室中的沉積前驅物)在適當溫度與壓力下反應，而形成含矽氧與碳膜112，該溫度在實施例中為例如低於100℃的反應溫度，該壓力為例如約0.1 Torr至約10 Torr；0.5至6 Torr的總腔室壓力等。大體而言，含矽氧與碳膜可以是含矽與氧層。在沉積期間，可藉由支撐晶圓的晶圓底座調整晶圓(即加熱或冷卻晶圓)達約0℃至約150℃的溫度。實施例中，針對無碳的含矽氮與氫層形成製程或含矽氧與碳層形成製程描述的製程參數也應用到其他層。在揭示的實施例中，含矽氧與碳覆蓋層(或含矽與氧覆蓋層)的厚度大於約100Å、150Å或200Å。
含矽與碳前驅物可包括具有直接Si-C鍵結的有機矽烷化合物及/或具有Si-O-C鍵結之化合物。有機矽烷矽前驅物之範例除其他之外特別可包括二甲基矽烷、三甲基矽烷、四甲基矽烷、四甲基二矽氧烷、二乙基矽烷、正矽酸甲酯(tetramethylorthosilicate)、正矽酸乙酯(tetraethylorthosilicate)、八甲基三矽氧烷 (octamethyltrisiloxane)、八甲基環四矽氧烷(octamethylcyclotetrasiloxane)、四甲基二甲基二甲氧基二矽烷(tetramethyldimethyldimethoxydisilane)、四甲基環四矽氧烷(tetramethylcyclotetrasiloxane)、二甲基二甲氧基矽烷(dimethyldimethoxysilane)、二乙基甲基矽烷、甲基三乙氧基矽烷、苯基二甲基矽烷與苯基矽烷。含矽與碳前驅物在導入沉積腔室之前或期間可與載氣混合。載氣可為非活性氣體，該氣體不會過度地干擾基材上氧化物膜的形成。載氣的範例除了其他氣體之外特別包括氦、氖、氬、氮(N2)與氫(H2)。
實施例中，形成第二層(覆蓋層)之後無需固化操作去防止一旦暴露至空氣後膜性質隨時間發展。但仍可執行固化以使膜堆疊轉變成含矽與氧層。膜堆疊可在方法100完成後固化。固化階段涉及將含矽氮與氫層暴露至含臭氧的大氣。在實施例中，臭氧在基材處理區域外生成，並且流進基材處理區域。在本發明的不同實施例中，可(或可不)施加電漿功率至基材處理區域而進一步激發臭氧之大氣。在實施例中，缺乏電漿避免了原子氧生成，該原子氧可能修飾接近表面的網絡並且阻撓次表面氧化。減少氮與增加氧並非僅在表面附近發生，還會在基材區域發生，這是由於相對穩定的臭氧能夠滲透矽氮與氫層的網絡之能力所致。在實施例中，於臭氧固化的另一階段，接著可施加電漿至基材處理區域，以激發臭氧大氣。
接著，描述應用至固化操作的各個參數。沉積基材可留在基材處理區域中以供固化，或該基材可傳送到導入含臭氧之大氣的不同腔室。不同實施例中，任一/兩個階段期間基材的固化溫度可為約300℃或更低，約250℃或更低，約225℃或更低，或者約200℃或更低。在不同實施例中，該基材之溫度可以為約室溫(25℃)或更高，約50℃或更高，約100℃或更高，約125℃或更高，或約150℃或更高。根據額外揭示的實施例，任一上限可與任一下限結合以形成基材溫度的額外範圍。固化操作期間臭氧(僅臭氧的貢獻)進入基材處理區域的流速在所揭示的實施例中可大於500 sccm、大於1 slm或大於2 slm。固化操作期間的臭氧分壓在所揭示的實施例中可為約20 Torr或更大，約30 Torr或更大，約50 Torr或更大，或約100 Torr或更大。
固化操作將含矽氮與氫層修飾成含矽與氧層。該含矽與氧層可轉變成氧化矽層，這是藉由在含氧環境中於相對高溫下退火基材或藉由在甚低的溫度下將基材暴露至水而完成。當導入含氧大氣時，沉積基材可留在相同的基材處理區域中以供固化，或該基材可傳送到導入含氧之大氣的不同腔室。含氧大氣可包括一或多種含氧氣體，該等含氧氣體除了其他含氧氣體外特別諸如為氧氣(O2)、臭氧(O3)、水蒸氣(H2O)、過氧化氫(H2O2)與氮氧化物(NO、NO2等)。含氧大氣也可包括自由基氧與氫氧物種，諸如原子氧(O)、氫氧化物(OH)等， 該等物種可遠端生成並且輸送進入基材腔室。也可存在含氧物種的離子。基材的氧退火溫度在不同實施例中可為約1100℃或更低、約1000℃或更低、約900℃或更低，或者是約800℃或更低。基材的溫度在不同實施例中可為約500℃或更高，約600℃或更高、約700℃或更高，或者是約800℃或更高。再一次，根據額外揭示的實施例，任一上限可與任一下限結合以形成基材溫度的額外範圍。
以替代方式或結合方式，可藉由將含矽與氧層暴露於潮濕環境而使含矽與氧層轉變成氧化矽。在所揭示的實施例中，可於相同的區域中提供該潮濕環境以用於固化，或者可將該基材移動至分開的處理站。本發明的實施例中，該潮濕環境可具有一相對濕度，該相對濕度為大於50%、大於60%、大於70%、大於75%、大於80%或大於85%。在實施例中，基材溫度可以介於室溫(25℃)與約100℃之間，介於約40℃與約95℃之間，介於約50℃與約90℃之間，介於60℃與約90℃之間，或介於約70℃與約90℃之間。在本發明的實施例中，濕氣處理(humidity treatment)的歷時可低於2分鐘、低於5分鐘、低於10分鐘、低於30分鐘或低於一小時。
臭氧固化操作一般發生在比濕氣處理更高的基材溫度下。實施例中，固化操作與濕氣處理可在分開的腔室/站中執行，因為這些低溫有點難以精確地在相同區域中調整。納入此述的低溫濕氣處理使得高溫氧大氣退火(例 如大約400℃左右或更高)為非必要。在本發明的實施例中，濕氣處理與固化操作結合而完成了氧化矽轉變製程。其他實施例中，只有濕氣處理用於執行轉變製程。在任一情況中，移除高溫氧處理使轉變製程得以發生而不氧化底下的層。缺乏在氧大氣中的高溫退火使積體電路製造業者能夠維持在氧化預算內。移除這些較高溫氧退火改善了積體電路元件的產率與表現。雖此述的本發明已免除了氧化退火，然而在實施例中仍可納入高溫惰性退火以使氧化矽膜緻密。在惰性環境中的高溫退火被計入熱預算，但不計入更特定的氧化預算，前述預算之各者與特定流程相關並且依該特定流程而決定。
固化、退火與濕氣處理的含臭氧大氣提供氧以將含矽氮與氫膜轉變成氧化矽(SiO2)膜。將立即描述替代性的濕氣處理。
用於沉積含矽氮與氫層及覆蓋層的基材可為圖案化基材且可具有複數個間隙以用於基材上形成的元件部件(例如電晶體)之間隔與結構。該等間隙可具有一高度與寬度，該高度與寬度界定該高度對寬度(即H/W)的深寬比(AR)，該AR遠大於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，10：1或更大，11：1或更大，12：1或更大等。許多範例中，高AR是由於小間隙寬度，該寬度範圍為約90 nm至約22 nm或更小，例如低於90 nm、65 nm、50 nm、45 nm、32 nm、22 nm、16 nm等。因為該含矽氮與氫層可流動，該層能 夠填充高深寬比的間隙，而不會在填充材料的中心周圍建立空隙或脆弱縫線。例如，沉積可流動材料在完全填充之前，較不可能預先阻塞間隙頂部，而在間隙中間留下空隙。
隨後將基材從含臭氧大氣移出，且將含矽與氧層浸漬於包含氧與氫的液體溶液中，以完成氧化矽層的轉變。本發明的實施例中，由於存在液體溶液步驟，進一步退火可能並非必須。如此述般臭氧固化及在液體浴中浸漬所得的膜在基材上(包括基材間隙)產生氧化矽層。如前文所記載，氧化矽層相較於以含碳前驅物形成的類似層具有較少孔隙與較少的在體積上的減少，該等以含碳前驅物形成的類似層在熱處理步驟前於層中存在顯著量的碳。許多情況中，體積的減少夠輕微(例如約15 vol.%或更低)，足以避免用於填充、癒合或以其他方式消除因縐縮的氧化矽而形成在間隙中的空間的後熱處理步驟。在一些實施例中，溝槽中的氧化矽層實質上無空隙。
在液體浴中浸漬該固化的膜之操作期間，液體浴、基材與固化的膜可保持在相同溫度。實施例中，液體浴可介於室溫(25℃)與約100℃之間，介於約40℃與約95℃之間，介於約50℃與約90℃之間，介於60℃與約90℃之間，或介於約70℃與約90℃之間。液體浴浸泡的歷時在本發明的實施例中可低於2分鐘、低於5分鐘、低於10分鐘、低於30分鐘或低於一小時。在本發明的實施例中，已發現，一旦如此述般依序先以臭氧固化後以 液體浴處理含矽氮與氫層，則後續的高溫氧退火為非必要。發明人已經進一步發現，在一些情況中液體浴可足以將含矽與氧層轉化成氧化矽。欲達成氧化矽，在先前的臭氧固化為非必要，而隨後的高溫氧退火也非必要。
液體浴或溶液包含氧與氫且可包括水、過氧化氫或氫氧化銨之一或多者。矽與氧膜浸漬在液體溶液中，且在一些實施例中，該基材可在浸漬操作期間沉入液體溶液中。實施例中，液體溶液可以是SC1或SC2浴。該液體溶液可包含去離子水、至少10%的氫氧化銨與至少10%的過氧化氫。所有的百分比在此都是以體積計。該液體溶液可包含去離子水、至少10%的鹽酸與至少10%的過氧化氫。可建立其他含有氧與氫二者的液體浴。發明人也已經發現，當pH降低至酸性範圍或升高至鹼性範圍時，轉變至氧化矽的轉變率增加。描述示範性氧化矽沉積系統期間，可導入額外的製程參數。
示範性氧化矽沉積系統
可實施本發明實施例的沉積腔室除其他類型的腔室外特別可包括高密度電漿化學氣相沉積(HDP-CVD)腔室、電漿強化化學氣相沉積(PECVD)腔室、次大氣壓化學氣相沉積(SACVD)腔室與熱化學氣相沉積腔室。可實施本發明之實施例的CVD系統的特定範例包括CENTURA ULTIMA® HDP-CVD腔室/系統與PRODUCER® PECVD腔室/系統，此二者可購自美國加 州Santa Clara的應用材料公司。
可與本發明之示範方法一併使用的基材處理腔室的範例可包括顯示於及描述於共同讓渡給Lubomirsky等人的美國臨時專利申請案第60/803,499號中的該等腔室，該案於2006年5月30日提出申請，且發明名稱為「PROCESS CHAMBER FOR DIELECTRIC GAPFILL」，該案全文在此併入作為參考，以供所有目的之用。額外的示範性系統可包括顯示於及描述於美國專利第6,387,207號與第6,830,624號中的該等系統，該等專利之全文亦在此併入作為參考，以供所有目的之用。
沉積系統的實施例可結合至較大的製造系統，以生產積體電路晶片。第2圖圖示根據所揭示之實施例之一個此類沉積、烘烤及固化腔室之系統200。在該圖中，一對FOUP(前開式晶圓盒)202供給基材(例如300 mm直徑的晶圓)，在該等基材放進晶圓處理腔室208a-f之一者前，基材是由機械手臂204接收並且放置到低壓固持區域206。第二機械手臂210可用於從固持區域206輸送基材晶圓至處理腔室208a-f並且往回輸送。
處理腔室208a-f可包括一或多個用以在基材晶圓上沉積、退火、固化及/或蝕刻可流動介電膜的的系統部件。在一個配置方式中，兩對處理腔室(例如，208c-d及208e-f)可用於沉積可流動介電材料於基材上，而第三對處理腔室(例如，208a-b)可用於退火沉積的介電質。在另一配置方式中，相同的兩對處理腔室(例如208c-d 及208e-f)可經裝設以在基材上沉積及退火可流動介電膜，同時第三對腔室(例如208a-b)可用於UV或電子束固化沉積的膜。另一配置方式中，所有三對腔室(例如208a-f)可經裝設以於基材上沉積及固化可流動的介電膜。尚有另一配置方式，兩對處理腔室(例如208c-d及208e-f)可用於沉積及以UV固化或電子束固化可流動介電質，同時第三對腔室(例如208a-b)可用於退火介電膜。所述製程的任何一或多者可在與不同實施例中所示的製造系統分開的腔室上執行。
此外，一或多個製程腔室208a-f可被裝設成濕式處理腔室。該等製程腔室包括在含水分(moisture)的大氣下加熱該可流動介電膜。因此，系統200之實施例可包括濕式處理腔室208a-b及退火處理腔室208c-d，以在沉積的介電膜上執行濕式及乾式退火二者。
第3A圖是根據所揭示的實施例之基材處理腔室300。遠端電漿系統(RPS)310可處理氣體，隨後該氣體行進穿過氣體入口組件311。在氣體入口組件311中可見兩個個別的氣體供給通道。第一通道312搭載穿過遠端電漿系統(RPS)310的氣體，而第二通道313繞過RPS 310。在揭示的實施例中，第一通道312可用於製程氣體而第二通道313可用於處理氣體(treatment gas)。圖中圖示蓋(或導電的頂部部分)321及穿孔隔件353之間有絕緣環324，該絕緣環使AC電位得以相對於穿孔隔件353施加到蓋321。製程氣體行進穿過第一通道312進入腔 室電漿區域320，且可單獨在腔室電漿區域320中(或者與RPS 310相結合)的電漿裡受到激發。在此腔室電漿區域320及/或RPS 310之結合可指遠端電漿系統。穿孔隔件(也稱為噴頭)353將腔室電漿區域320分隔噴頭353下方的基材處理區域370。噴頭353使電漿得以存在於腔室電漿區域320中，以避免直接於基材處理區域370中激發氣體，同時依然使激發的物種得以從腔室電漿區域320行進至基材處理區域370。
噴頭353定位在腔室電漿區域320與基材處理區域370之間，且使電漿流出物(前驅物或其他氣體的受激發的衍生物)在腔室電漿區域320建立，而穿過複數個橫切板厚的透孔(through hole)356。噴頭353亦具有一或多個中空空間351，該空間可被蒸氣或氣態形式的前驅物(諸如含矽前驅物)填充，並且穿過小孔洞355進入基材處理區域370但不直接進入腔室電漿區域320。在此揭示的實施例中，噴頭353比透孔356的最小直徑350的長度還厚。為了維持從腔室電漿區域320穿透至基材處理區域370的受激發物種具顯著濃度，可藉由形成透孔356之較大的直徑部分使該較大的直徑部分穿過噴頭353達某一程度(part way)，而限制透孔最小直徑350的長度326。在所揭示的實施例中，透孔356的最小直徑350之長度可與透孔356的最小直徑相同數量級，或者為較小的數量級。
在所示的實施例中，一旦製程氣體受到腔室電漿區域 320中的電漿激發，噴頭353可(經由透孔356)分配製程氣體，該等製程氣體含有氧、氫及/或氮，及/或此類製程氣體的電漿流出物。在實施例中，經由第一通道312導入RPS 310中及/或腔室電漿區域320中的製程氣體可含有氧(O2)、臭氧(O3)、N2O、NO、NO2、NH3、包括N2H4的NxHy、矽烷、乙矽烷(disilane)、TSA及DSA之一或多者。該製程氣體亦可包括諸如氦氣、氬氣、氮氣(N2)等之類的載氣。第二通道313亦可傳遞製程氣體及/或載氣，及/或膜固化氣體(例如O3)，該膜固化氣體用於從生長中的膜或剛沉積的膜中移除非期望的成分。電漿流出物可包括製程氣體的離子化或中性衍生物，且在此電漿流出物亦可指自由基氧前驅物及/或自由基氮前驅物，前述二前驅物所指的是所導入的製程氣體之原子的組分。
在實施例中，透孔356的數量可介於約60個至約2000個之間。透孔356可具有多種形狀，但最容易做成圓形。在所揭示的實施例中，透孔356的最小直徑350可介於約0.5 mm與約20 mm之間，或介於約1 mm與約6 mm之間。在選擇透孔的截面形狀上，亦有範圍，截面可做成錐形、圓柱形或該二種形狀的組合。不同實施例中，用於將氣體導進處理區域370的小孔洞355數量可介於約100與約5000之間，或介於約500與約2000之間。小孔洞355的直徑可介於約0.1 mm與約2 mm之間。
第3B圖是根據所揭示的實施例與處理腔室一併使用 的噴頭353之底視圖。噴頭353對應第3A圖中所圖示的噴頭。透孔356被繪成在噴頭353底部處具有較大的內徑(ID)，而在頂部處具有較小的ID。小孔洞355實質上在噴頭表面上均勻分佈，甚至分佈在透孔356之間，相較於此述的其他實施例，這種分佈方式助於提供更均勻的混合。
當穿過噴頭353中的透孔356抵達的電漿流出物與源自中空空間351穿過小孔洞355抵達的含矽前驅物結合時，在基材處理區域370內示範性的膜建立在由底座(圖中未示)支撐的基材上。雖可將基材處理區域370裝配成支援電漿以供諸如固化之類的其他製程所用，然而在生長示範性膜期間無電漿存在。
電漿既可在噴頭353上方的腔室電漿區域320中點燃，亦可在噴頭353下方的基材處理區域370點燃。電漿存在於腔室電漿區域320中，以從含氮與氫之氣體的流入中產生自由基氮前驅物。於處理腔室之導電頂部部分321及噴頭353之間施加一般在射頻(RF)範圍的AC電壓，以在沉積期間於腔室電漿區域320中點燃電漿。RF電源供應器產生13.56 MHz的高RF頻率，但亦可產生單獨其他頻率或者與13.56 MHz頻率結合的頻率。
當於第二固化階段開啟基材處理區域370中的底部電漿或該底部電漿清潔接壤基材處理區域370的內部表面時，頂部電漿可處於低功率或無功率。藉由在噴頭353及底座(或腔室底部)之間施加AC電壓，而點燃基材 處理區域370中的電漿。清潔氣體可在電漿存在時導入基材處理區域370。
底座可具有熱交換通道，熱交換流體流過該熱交換通道中以控制基材溫度。此配置方式使基材溫度得以冷卻或加熱，以維持相對低的溫度(從室溫直到約120℃)。熱交換流體可包含乙二醇與水。底座的晶圓支撐淺盤(較佳為鋁、陶瓷或前述材料之組合)亦可被電阻式加熱以達成相對高的溫度(從約120℃直到約1100℃)，此加熱是藉由使用嵌入式單迴路嵌入的加熱器元件達成，該元件設以造成平行的同心圓形式的兩個完整迴轉。加熱器元件的外部可繞於鄰接支撐淺盤的周邊處，同時內部繞於具有較小半徑的同心圓的路徑上。至加熱器元件的配線穿過底座的心柱。
基材處理系統是由系統控制器控制。在示範性實施例中，系統控制器包括硬碟機、軟碟機及處理器。處理器含有單板電腦(SBC)、類比數位輸入/輸出板、介面板及步進馬達控制板。CVD系統的各部件符合Versa Modular European(VME)標準，該標準界定電路板、介面卡插件箱(card cage)及連結器規格與類型。VME標準亦界定匯流排結構為具有16位元資料匯流排及24位元位址匯流排。
系統控制器控制所有沉積系統的活動。系統控制器執行系統控制軟體，該軟體是儲存在電腦可讀媒體中的電腦程式。該媒體較佳為硬碟，但該媒體也可以是其他種 類的記憶體。電腦程式包括指令集，該等指令集指定時間、氣體混合、腔室壓力、腔室溫度、RF功率層級、基座(susceptor)位置及其他特定製程參數。儲存在其他記憶體元件(其他記憶體元件包括例如軟碟或其他適合的驅動器)上的其他電腦程式亦可用於指示系統控制器。
可使用由系統控制器執行的電腦程式產品實施用於在基材上沉積膜堆疊(例如依序沉積含矽氮與氫層而隨後沉積含矽氧與碳層)、將膜轉變成氧化矽的製程或者用於清潔腔室的製程。電腦程式編碼可用任何習知電腦可讀的程式語言撰寫，例如68000組語、C、C++、Pascal、Fortran或其他程式語言。使用習知的文件編輯器將適合的程式編碼編入單一檔案或多重檔案，並且儲存或收錄於電腦可使用媒體(如電腦的記憶體系統)。倘若編入的編碼內文是高階語言，則編譯編碼，而所得的編譯編碼隨後與預先編譯的Microsoft Windows®函式庫常式之目的碼連結。為了執行該連結、編譯的目的碼，系統使用者援用該目的碼，使電腦系統載入記憶體中的編碼。CPU隨後讀取並且執行該編碼，以執行程式中辨識的任務。
使用者與控制器之間的介面經由平板接觸感應顯示器。在較佳實施例中，使用兩個顯示器，一個安裝在清潔室壁以供操作者使用，另一個在壁後以供維修技術人員使用。兩個顯示器可同時顯示相同資訊，該情況中，一次僅有一個接受輸入。為了選擇特定的螢幕或功能，操作者接觸該接觸感應顯示器的指定區域。接觸區域改 變該區域的強調色彩，或呈現新的選單或螢幕，以確認操作者和接觸感應顯示器之間的溝通。取代接觸感應顯示器，或者是除了接觸感應顯示器之外，可使用其他裝置，例如鍵盤、滑鼠或其他指示或溝通裝置，以讓使用者與系統控制器溝通。
在此所使用的「基材」可為具有(或不具有)形成在上面的多個層的支撐基材。該支撐基材可為有各種摻雜濃度及摻雜輪廓的絕緣體或半導體，可例如為用在積體電路製造上的該類型的半導體基材。「氧化矽」層可包括次要濃度的其他元素組分，諸如氮、氫、碳與類似元素。在一些實施例中，氧化矽基本上由氧與矽構成。「前驅物」之用語是用於指任何參與反應從表面移除材料或沉積材料在表面上的製程氣體。處於「激發態」的氣體描述其中至少有一些氣體分子處於振動型式的激發、解離及/或離子化的狀態的氣體。氣體(或前驅物)可以是兩種或兩種以上氣體(或前驅物)的組合。「自由基前驅物」是用於描述參與反應從表面移除材料或沉積材料在表面上的電漿流出物(離開電漿、處於激發態的氣體)。「自由基氮前驅物」是一種含有氮的自由基前驅物，而「自由基氫前驅物」是一種含有氫的自由基前驅物。「惰氣」一詞是指在蝕刻或被併入膜中時不形成化學鍵結的任何氣體。示範性的惰氣包括稀有氣體，但可包括其他氣體，只要當(一般而言)在膜中補捉到痕量的該氣體時不形成化學鍵結即可。
全文中所用的「溝槽」(trench)之用語毫無暗指意味地是指蝕刻過的幾何形狀具有大的水平深寬比。由表面上方所視，溝槽可顯現圓形、卵形、多邊形、矩形或各種其他形狀。「通孔」(via)之用語用於指低深寬比溝槽，該通孔可或可不被金屬填充而形成垂直的電連接。如在此所用，共形層指的是表面上與該表面形狀相同的大體上均勻的材料層，即，該層的表面與受覆蓋的表面大體上平行。此技術領域中具通常知識者將瞭解沉積的材料可能不會100%共形，而因此「大體上」一詞允許可接受的容忍值。
已在此描述數個實施例，發明所屬技術領域中具有通常知識者應知可使用多種修飾例、替代架構與等效例而不背離所揭示之實施例的精神。此外，說明書中不描述多種習知製程與元件，以避免不必要地混淆了本發明。故，上文中的描述不應被視為對本發明範疇之限制。
當提供一範圍的數值時，除非文本中另外清楚指明，應知亦具體揭示介於該範圍的上下限值之間各個區間值至下限值單位的十分之一。亦涵蓋了所陳述數值或陳述範圍中之區間值與陳述範圍中任何另一陳述數值或區間值之間的每個較小範圍。這些較小範圍的上限值與下限值可獨立地被包含或排除於該範圍中，且其中在該較小範圍內包含任一個極限值、包含兩個極限值，或不含極限值的各範圍也涵蓋於本發明內，取決於在該陳述的範圍中的任何特別排除之限制。在所陳述之範圍包括極限 值的一者或兩者之處，也包括該些排除其中任一者或兩者被包括的極限值的範圍。
在此與如附申請專利範圍中所使用之單數形式「一」與「該」等用語也包括複數形式，除非文本中另外清楚指明。因此，舉例而言，「一種製程」所指的製程包括複數個此類製程，而「該前驅物」所指的包括一或多種前驅物及該領域技術人士所熟知的該等材料之等效例等。
同樣，申請人希望此說明書與下述申請專利範圍中所用的「包括」與「包含」等用語是指存在所陳述之特徵、整體、部件或步驟，但該等用語不排除存在或增加一或多種其他特徵、整體、部件、步驟、動作或群組。
100‧‧‧方法
102-112‧‧‧處理步驟
200‧‧‧處理系統
202‧‧‧FOUP
204、210‧‧‧機械手臂
206‧‧‧低壓固持區域
208a-f‧‧‧處理腔室
300‧‧‧基材處理腔室
310‧‧‧遠端電漿系統
311‧‧‧氣體入口組件
312、313‧‧‧通道
320‧‧‧腔室電漿區域
321‧‧‧蓋
324‧‧‧絕緣環
326‧‧‧長度
350‧‧‧直徑
351‧‧‧中空空間
353‧‧‧穿孔隔件
355‧‧‧小孔洞
356‧‧‧透孔
370‧‧‧基材處理區域
藉由參考說明書之其餘部分及圖式，可進一步瞭解本發明的本質與優點，在該等圖式中，相似的元件符號用於全部多幅圖式中以指類似部件。一些例子中，次符號與元件符號相連且置於破折號後，以標注多個類似部件之一者。當參考元件符號而不對現存次符號詳細規定時，申請人希望是指所有此類多個類似部件。
第1圖是流程圖，說明用於根據本發明之實施例製作氧化矽膜的所選擇的步驟。
第2圖圖示根據本發明實施例的基材處理系統。
第3A圖圖示根據本發明實施例的基材處理腔室。
第3B圖圖示根據本發明實施例的氣體分配噴頭。
100‧‧‧方法
102-112‧‧‧處理步驟

Claims (19)

  1. 一種在一基材上形成一氧化矽層的方法，該方法包含以下步驟：形成包含矽、氮與氫的一第一層，該步驟藉由以下步驟完成：將一無激發的前驅物流進一第一遠端電漿區域以產生一自由基前驅物；在一第一無電漿的基材處理區域中將一無碳的含矽前驅物結合該自由基前驅物；及沉積一無碳的含矽氮與氫層覆於該基材上；及形成包含矽與氧的一第二層，該步驟藉由以下步驟完成：將一無激發的含氧前驅物流進一第二遠端電漿區域以產生一自由基氧前驅物；將一含矽與碳前驅物與該自由基氧前驅物在一第二無電漿的基材處理區域中結合；及沉積一含矽氧與碳的覆蓋層覆於該無碳的含矽氮與氫層上。
  2. 如請求項1所述之方法，其中在形成該第一層與形成該第二層之間該基材不暴露至空氣。
  3. 如請求項1所述之方法，其中在形成該第一層後與形成該第二層前，從該第一無電漿的基材處理區域移除未反應的前驅物及反應副產物。
  4. 如請求項1所述之方法，其中該第一遠端電漿區域與該第二遠端電漿區域相同，且該第一無電漿的基材處理區域與該第二無電漿的基材處理區域相同。
  5. 如請求項1所述之方法，其中在形成該第一層與該第二層期間，該基材的一溫度為約0℃或更大至約225℃或更低。
  6. 如請求項1所述之方法，其中在形成該第二層之後不需要固化操作防止一旦暴露該基材至空氣後膜性質隨著時間發展。
  7. 如請求項1所述之方法，其中該含矽與碳前驅物包含以下物質之一者：二甲基矽烷、三甲基矽烷、四甲基矽烷、二乙基矽烷、正矽酸甲酯(tetramethylorthosilicate)、四甲基二矽氧烷、正矽酸乙酯(tetraethylorthosilicate)、八甲基三矽氧烷(octamethyltrisiloxane)、八甲基環四矽氧烷(octamethylcyclotetrasiloxane)、四甲基二甲基二甲氧基二矽烷 (tetramethyldimethyldimethoxydisilane)、四甲基環四矽氧烷(tetramethylcyclotetrasiloxane)、二甲基二甲氧基矽烷(dimethyldimethoxysilane)、二乙基甲基矽烷、甲基三乙氧基矽烷、苯基二甲基矽烷與苯基矽烷之一者。
  8. 如請求項1所述之方法，進一步包含以下步驟：在一含臭氧大氣中固化該第一層與該第二層，以將該第一層與該第二層轉變成一含矽與氧層。
  9. 如請求項8所述之方法，其中在該固化操作期間，該基材的一溫度為約75℃或更高至約225℃或更低。
  10. 如請求項8所述之方法，進一步包含以下步驟：將該含矽與氧層暴露至一潮濕環境，該潮濕環境具有至少50%的相對濕度，以將該含矽與氧層轉變成一氧化矽層。
  11. 如請求項10所述之方法，其中在該暴露操作期間，該基材的一溫度為約25℃或更高至低於100℃。
  12. 如請求項10所述之方法，其中該氧化矽層基本上由矽與氧構成。
  13. 如請求項1所述之方法，其中該第二層的一厚度介於約100Å與約300Å之間。
  14. 如請求項1所述之方法，其中該無碳的含矽氮與氫層在沉積期間可流動。
  15. 如請求項1所述之方法，其中該基材經圖案化並且具有一溝槽，該溝槽具有約50 nm或更低的一寬度。
  16. 如請求項1所述之方法，其中該無激發的前驅物包含氮且該自由基前驅物是一自由基氮前驅物。
  17. 如請求項1所述之方法，其中該無激發的前驅物包含N2H2、NH3、N2與H2之至少一者。
  18. 如請求項1所述之方法，其中該無碳的含矽前驅物包含N(SiH3)H2、N(SiH3)2H或N(SiH3)3之一者。
  19. 如請求項1所述之方法，進一步包含以下步驟：在形成該第一層與形成該第二層的該等操作之間從該第一無電漿的基材處理區域移除製程流出物。
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