TW201310529A - 減少脫氣所用的表面處理及沉積 - Google Patents

減少脫氣所用的表面處理及沉積 Download PDF

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TW201310529A
TW201310529A TW101124223A TW101124223A TW201310529A TW 201310529 A TW201310529 A TW 201310529A TW 101124223 A TW101124223 A TW 101124223A TW 101124223 A TW101124223 A TW 101124223A TW 201310529 A TW201310529 A TW 201310529A
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layer
precursor
nitrogen
free
carbon
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Jing-Mei Liang
Xiaolin Chen
Nitin K Ingle
Shankar Venkataraman
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Applied Materials Inc
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Abstract

在此描述一種形成介電層的方法。該方法首先透過自由基成分的化學氣相沉積(CVD)沉積含矽氮與氫(聚矽氮烷)層。該含矽氮與氫層是透過將自由基前驅物(在遠端電漿中激發)與無激發的無碳的矽前驅物結合而形成。氧化矽覆蓋層可由一部分的無碳的含矽氮與氫層形成，以避免底下的層在轉換成氧化矽之前該層的性質在時間上發展。或者，該氧化矽覆蓋層形成為覆於該含矽氮與氫層上。任一形成方法皆涉及在基材處理區域內形成原地電漿。

Description

減少脫氣所用的表面處理及沉積 【對相關申請案之交互參照】
此申請案主張美國臨時專利申請案61/508,355之權益，該臨時申請案是在2011年7月15日提出，發明名稱為「SURFACE TREATMENT AND DEPOSITION FOR REDUCED OUTGASSING」，該申請案在此以參考形式併入，以供所有目的之用。
本發明是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，且正開發及實行新設備以製做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，他們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。該材料大體上由矽氮烷類型的層轉換成氧化矽，該矽氮烷類型的膜含有矽、氮、與氫。含有矽、氮、與氫的層一般在高溫下於含氧環境中轉換成氧化矽。來自環境的氧替換氮與氫以建立氧化矽層。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層。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可透過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層。層性質(包括密度)可能在時間中會稍微改變，直到含矽氮烷層轉變成氧化矽為止。控制層性質的發展(evolve)改善使用這些層的元件的製造能力。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。
在此描述一種形成介電層的方法。該方法首先透過自由基成分的化學氣相沉積(CVD)沉積含矽氮與氫(聚矽氮烷)層。該含矽氮與氫層是透過將自由基前驅物(在遠端電漿中激發)與無激發的無碳的矽前驅物結合而形成。氧化矽覆蓋層可由一部分的無碳的含矽氮與氫層形成，以避免底下的層在轉換成氧化矽之前該層的性質在時間上發展。或者，該氧化矽覆蓋層形成為覆於該含矽氮與氫層上。任一形成方法皆涉及在基材處理區域內形成原地電漿。
本發明的實施例包括在基材上形成介電層的方法。該等方法包括下述依序的步驟：(1)在含有該基材的第一基材處理區域中，於該基材上形成無碳的含矽氮與氫層， 以及(2)在該無碳的含矽氮與氫層上形成氧化矽覆蓋層。形成該無碳的含矽氮與氫層包括以下步驟：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，在該第一基材處理區域中將無碳的含矽前驅物與該自由基前驅物結合，以及沉積無碳的含矽氮與氫層覆於該基材上。在形成該無碳的含矽氮與氫層之操作期間，該第一基材處理區域無電漿。該無碳的含矽氮與氫層在沉積期間可流動。形成該氧化矽覆蓋層包括以下步驟：將含氧前驅物流進含有該基材的第二基材處理區域，將含矽前驅物流進該第二基材處理區域，在該第二基材處理區域中從該含氧前驅物與該含矽前驅物形成電漿，以及沉積該氧化矽覆蓋層覆於該無碳的含矽氮與氫層上。
本發明的實施例包括在基材上形成介電層的方法。該等方法包括下述依序的步驟：(1)在含有該基材的第一基材處理區域中，於該基材上形成無碳的含矽氮與氫層，以及(2)處理該無碳的含矽氮與氫層，以將該無碳的含矽氮與氫層的一部分轉換成氧化矽覆蓋層。形成該無碳的含矽氮與氫層包括以下步驟：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，在該第一基材處理區域中將無碳的含矽前驅物與該自由基前驅物結合，以及沉積無碳的含矽氮與氫層覆於該基材上。在形成該無碳的含矽氮與氫層之操作期間，該第一基材處理區域無電漿。該無碳的含矽氮與氫層在沉積期間可流動。處理該無碳的含矽氮與氫層包括以下步驟：將含氧前驅物流進 含有該基材的第二基材處理區域，在該第二基材處理區域中從該含氧前驅物形成電漿，以及將該無碳的含矽氮與氫層的一部分轉換成該氧化矽覆蓋層。
額外的實施例與特徵部份在隨後的實施方式中提出，而部份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，或者可由操作所揭露的實施例而學得。可透過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露的實施例之特徵與優點。
在此描述一種形成介電層的方法。該方法首先透過自由基成分的化學氣相沉積(CVD)沉積含矽氮與氫(聚矽氮烷)層。該含矽氮與氫層是透過將自由基前驅物(在遠端電漿中激發)與無激發的無碳的矽前驅物結合而形成。氧化矽覆蓋層可由一部分的無碳的含矽氮與氫層形成，以避免底下的層在轉換成氧化矽之前該層的性質在時間上發展。或者，該氧化矽覆蓋層形成為覆於該含矽氮與氫層上。任一形成方法皆涉及在基材處理區域內形成原地電漿。
已發現將自由基成分CVD的含矽氮與氫層定位在氧化矽覆蓋層下方減少及/或消除脫氣以及伴隨的層性質的發展。沒有氧化矽覆蓋層，層的性質與化學當量可能隨著時間改變。由於含矽物種、氨氣、與類似物的脫氣， 這些層在時間上發展。由於吸收存在於一般製造設施內的周圍氣氛中的水或其他成分，性質也可能發展。改變層性質可能會因需要嚴密控制層形成與其他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脫氣，但仍容許底下的含矽氮與氫層轉變成含矽與氧層且轉變成氧化矽。
已發現根據在此所含的方法以含氧化矽覆蓋層覆蓋自由基成分的CVD層在基材暴露至一般清潔室氣氛時顯現不會發展之性質。現在，將描述關於形成氧化矽覆蓋層的方法與系統的額外細節。
第一示範性介電質堆疊製程
第1圖是流程圖，顯示根據本發明之實施例製做介電層堆疊的方法100中所選步驟。方法100包括提供無碳的含矽前驅物至基材處理區域102。一些實施例中，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。隨後僅透過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。缺乏碳減少了沉積層的縐縮。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。沉積層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，這些額外氣體可做為載氣、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，該解離可特別透過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，以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、以及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。添加氧源預先使層載有氧，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一區段中生成，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無碳的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，且可能透過噴頭中的穿孔(aperture)侵入基材處理區域上。在感應耦合電漿的情況中，例如可在基材處理區域內啟動少量的離子化。大體而言，低強度的電漿可在基材處理區域中建立，而不至於損害形成的層的可流動之本質。在建立自由基氮前驅物期間離子密度遠低於遠端/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層106。多個實施例中，所沉積的含矽氮與氫層具有可流動特性，此可流動特性與習知氮化矽(Si3N4)層沉積技術並不類似。形成期間可流動的本質使層得以在固化前流進狹窄的特徵中。
含矽氮與氫層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無碳的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露的每一實施例。在多個實施例中，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。
回到顯示於第1圖的特定範例，含矽氮與氫層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層中有顯著的氫成分及/或存在短鍊的聚矽氮烷聚合物。在形成層期間或之後，這些短鍊生長並且互成網絡，而形成更加緻密的介電材料。例如沉積層可具有矽氮烷形式的Si-NH-Si骨架，即無碳的Si-N-H層。當含矽前驅物與自由基前驅物二者皆無碳時，沉積的含矽氮與氫層也實質上無碳。當然，「無碳」並非必然意味該層缺乏甚至痕量的碳。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TEOS、TMDSO等)中可見的量。
該製程中的此點，在本發明的多個實施例中，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 反應的含矽前驅物、未反應的自由基氮前驅物、惰性的載氣以及來自層生長的反應產物。在所揭露的實施例中，可透過將惰性物種流進基材處理區域及/或通過排放通口排放而移動製程流出物。
該方法100也包括額外沉積氧化矽覆於含矽氮與氫層上，以避免底下的層的脫氣。氧化矽層在此是指氧化矽覆蓋層。氧化矽覆蓋層的形成可發生在相同的基材處理區域中，或該基材可傳送到分開的處理區域。本發明的多個實施例中，該基材可在傳送期間暴露至氣氛，或可維持在真空下。形成氧化矽覆蓋層的優點是，避免執行後續處理之前，含矽氮與氫層的膜性質在時間上發展。就此而言，期望在沉積氧化矽覆蓋層之前有可控制且可再現的基材暴露量。透過提供含氧前驅物至基材處理區域而啟動氧化矽覆蓋層的沉積108。含矽前驅物也流進基材處理區域109，且在基材的附近與含氧前驅物結合。電漿同步在基材處理區域中形成110，以形成氧化矽覆蓋層112。已使用遠端電漿(在基材處理區域外)沉積含矽氮與氫層，然而原地電漿(在基材處理區域內)用於沉積氧化矽覆蓋層。
含氧前驅物可包括分子氧(O2)及/或臭氧(O3)。較佳實施例中，含矽前驅物可包括正矽酸乙酯(TEOS)。大體而言，該含矽前驅物可包括正矽酸乙酯(TEOS)、八甲基三矽氧烷(octamethyltrisiloxane,OMTS)、八甲基環四矽氧烷(octamethylcyclotetrasiloxane,OMCTS)、 甲基二乙氧基矽烷(methyldiethoxysilane,MDEOS)、雙(叔丁基胺基)矽烷(bis(tertiary-butylamino)silane,BTBAS)、三甲基氨基矽烷(tridimethylaminosilane,TriDMAS)、三二甲基氨基矽烷(trisdimethylaminosilane,TrisDMAS)、甲矽烷(silane)、乙矽烷(disilane)、二氯矽烷、三氯矽烷、二溴矽烷、四氯化矽、四溴化矽、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,TMOS)、或前述前驅物之組合。施加至基材處理區域的電漿功率可為約1000 W或更低、約500 W或更低、或者是約300 W或更低。在本發明多個實施例中，施加至基材處理區域的電漿功率可為約50 W或更高，約100 W或更高，或者是約200 W或更高。電漿功率的該等上限可與該等下限結合以形成額外實施例。該電漿功率低於許多電漿強化化學氣相沉積(PE-CVD)製程，以基本上維持底下的含矽氮與氫層的結構。電漿頻率可以是13.56 MHz及/或350 KHz。視情況與含矽前驅物同時導入腔室的氣體包括氦氣及/或氬氣。氦氣或其他惰氣可用做為載氣，以遞送平常為液體的前驅物至基材處理區域。
可用介於約10 sccm至約1000 sccm之間的流速將該含氧前驅物導進腔室。可用介於約5 sccm至約1000 sccm之間的流速將該含矽前驅物導進腔室。可用介於約100 sccm至約20000 sccm之間的流速將該視情況任選的載氣(例如氦氣)導進腔室。進入腔室的含矽前驅物(例 如正矽酸乙酯)流速對載氣(例如氦氣)流速的比為約1：1或更高，諸如介於約1：1至約1：100之間。當含矽前驅物與含氧前驅物流進腔室以沉積氧化矽覆蓋層的同時，基材處理區域內的壓力可大於約500 mTorr(諸如介於約2 Torr至約10 Torr之間)，且腔室中基材支撐件的溫度可以介於約100℃至約250℃之間。在所揭露的實施例中，該溫度較佳為低於約250℃或低於約200℃。低基材溫度也是期望的，以保有含矽氮與氫層的結構。含矽前驅物與含氧前驅物可各別流入腔室一段時間，該段時間足以沉積厚度為約5 nm或更大的氧化矽覆蓋層，該厚度為約10 nm或更大、約20 nm或更大、或者約50 nm或更大。
第二示範性介電質堆疊製程
第2圖是一流程圖，該流程圖顯示根據本發明的實施例製做介電層堆疊的第二方法200的所選步驟。該方法200包括形成含矽氮與氫層，如參考第2圖所描述。因此，該方法包括提供無碳的含矽前驅物至基材處理區域202，該步驟無電漿激發且如先前所述的所有實施例。該方法進一步包括提供自由基前驅物至基材處理區域204，如先前所述。該自由基前驅物提供主要的激發，此述的主要的激發是在無電漿的基材處理區域中「斷裂」無碳的含矽前驅物以及產生沉積含矽氮與氫層於沉積基材上206的反應所需。再度提醒，所沉積的含矽氮與氫 層可具有可流動特性，此可流動特性與習知氮化矽(Si3N4)層沉積技術並不類似。形成含矽氮與氫層之後，可由基材處理區域移除製程流出物。製程流出物可包括任何未反應的含矽前驅物、未反應的自由基氮前驅物、惰性的載氣以及來自層生長的反應產物。在所揭露的實施例中，可藉由將惰性物種流進基材處理區域及/或藉由通過排放通口排放而移動製程流出物。
該方法200進一步包括額外處理該含矽氮與氫層，以由該含矽氮與氫層的一部分形成氧化矽。與第1圖的方法呈對比，此氧化矽覆蓋層是透過使用一些含矽氮與氫層的材料形成。但是，所形成的氧化矽覆蓋層的目的與第1圖相同：為了避免從底下的層脫氣。氧化矽覆蓋層的形成可發生在相同的基材處理區域，或該基材可被傳送至分開的處理區域。本發明的多個實施例中，該基材可在傳送期間暴露至氣氛，或可維持在真空下。形成氧化矽覆蓋層的優點是，避免執行後續處理之前，含矽氮與氫層的膜性質在時間上發展。就此而言，期望在形成氧化矽覆蓋層之前有可控制且可再現的基材暴露量。透過提供含氧前驅物至基材處理區域，而啟動氧化矽覆蓋層的形成208。電漿同步在基材處理區域中形成210，以使用來自含矽氮與氫膜的材料以及來自含氧前驅物的氧形成氧化矽覆蓋層112。已使用遠端電漿(在基材處理區域外)沉積含矽氮與氫層，然而原地電漿(在基材處理區域內)用於沉積氧化矽覆蓋層。
含氧前驅物可包括分子氧(O2)及/或臭氧(O3)。施加至基材處理區域的電漿功率可為約1000 W或更低、約500 W或更低、或者是約300 W或更低。在本發明多個實施例中，施加至基材處理區域的電漿功率可為約50 W或更高，約100 W或更高，或者是約200 W或更高。電漿功率的該等上限可與該等下限結合以形成額外實施例。該電漿功率低於許多電漿強化化學氣相沉積(PE-CVD)製程，以基本上維持底下的含矽氮與氫層的結構。電漿頻率可以是13.56 MHz及/或350 KHz。視情況與含矽前驅物同時導入腔室的氣體包括氦氣及/或氬氣。氦氣或其他惰氣可用做為載氣，以遞送平常為液體的前驅物至基材處理區域。
可用介於約10 sccm至約1000 sccm之間的流速將該含氧前驅物導進腔室。當含氧前驅物流進腔室以形成氧化矽覆蓋層的同時，基材處理區域內的壓力可大於約500 mTorr(諸如介於約2 Torr至約10 Torr之間)，且腔室中基材支撐件的溫度可以介於約100℃至約250℃之間。在所揭露的實施例中，該溫度較佳為低於約250℃或低於約200℃。低基材溫度也是期望的(類似低電漿功率)，以保有含矽氮與氫層的結構，故在進一步處理開始的同時可預測層性質。含矽前驅物與含氧前驅物可各別流入腔室一段時間，該段時間足以沉積厚度為約10 nm或更大的氧化矽覆蓋層，該厚度為約20 nm或更大、約50 nm或更大、或者約100 nm或更大。
在示範性方法100或200任一者完成後，層堆疊準備受到固化或退火。固化階段涉及將氧化矽覆蓋層與無碳的含矽氮與氫層暴露至含氧的氣氛。本發明的實施例中，該含氧氣氛可包括臭氧。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氧之氣氛的不同腔室。不同實施例中，基材的固化溫度可為約300℃或更低，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。根據額外揭露的實施例，任一上限可與任一下限結合以形成基材溫度的額外範圍。
固化操作將無碳的含矽氮與氫層修飾成含矽與氧層。該含矽與氧層可轉換成氧化矽層，這是透過在含氧環境中於相對高溫下退火基材而完成。當導入含氧氣氛時，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氣氛的不同腔室。含氧氣氛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)。含氧氣氛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。固化與退火操作的含氧氣氛提供氧，以將含矽氮與氫層轉換成氧化矽 (SiO2)層。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，根據額外揭露的實施例，任一上限可與任一下限結合以形成基材溫度的額外範圍。
用於沉積無碳的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。因為該無碳的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。
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(PE-CVD)腔室、次氣氛壓化學氣相沉積(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3圖顯示根據所揭露之實施例之一個此類沉積、烘烤及固化腔室之系統300。在該圖中，一對FOUP(前開式晶圓盒)302供給基材基材(例如300 mm直徑的晶圓)，在該等基材放進基材處理腔室308a-f之一者前，基材是由機械手臂304接收並且放置到低壓固 持區域306。第二機械手臂310可用於從低壓固持區域306傳輸基材晶圓至基材處理腔室308a-f並且往回傳輸。
基材處理腔室308a-f可包括一或多個用以在基材晶圓上沉積、退火、固化及/或蝕刻可流動介電層的系統部件。在一個配置方式中，兩對處理腔室(例如，308c-d及308e-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，308a-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308c-d及308e-f)可經裝設以在基材上沉積及退火可流動介電層，同時第三對腔室(例如308a-b)可用於UV或電子束固化沉積的層。另一配置方式中，所有三對腔室(例如308a-f)可經裝設以於基材上沉積及固化可流動的介電層。尚有另一配置方式，兩對處理腔室(例如308c-d及308e-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308a-b)可用於退火介電層。所述製程的任一者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，一個或更多個基材處理腔室308a-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)的氣氛下加熱該可流動介電層。因此，系統300之實施例可包括濕式處理腔室及退火處理腔室，以在沉積的介電層上執行濕式及乾式退火二者。
第4A圖是根據所揭露的實施例之基材處理腔室400。遠端電漿系統(RPS410)可處理氣體，隨後該氣體行進 穿過氣體入口組件411。在氣體入口組件411中可見兩個個別的氣體供給通道。第一通道412搭載穿過遠端電漿系統(RPS)410的氣體，而第二通道413繞過RPS 410。在揭露的實施例中，第一通道412可用於製程氣體而第二通道413可用於處理氣體(treatment gas)。圖中圖示蓋(或導電的頂部部分)421以及穿孔隔件(或噴頭)453之間有一絕緣環424，該絕緣環使AC電位得以相對於噴頭453施加到蓋421。製程氣體行進穿過第一通道412進入腔室電漿區域420，且可單獨在腔室電漿區域420中(或者與RPS410相結合)的電漿裡受到激發。在此腔室電漿區域420及/或RPS410之結合可指遠端電漿系統。穿孔隔件(也稱為噴頭)453將腔室電漿區域420分隔噴頭453下方的基材處理區域470。噴頭453使電漿得以存在於腔室電漿區域420中，以避免直接於基材處理區域470中激發氣體，同時依然使激發的物種得以從腔室電漿區域420行進至基材處理區域470。
噴頭453定位在腔室電漿區域420與基材處理區域470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420建立，而穿過複數個橫切板厚的透孔(through hole)456。噴頭453亦具有一或多個中空空間451，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，並且穿過小孔洞455進入基材處理區域470但不直接進入腔室電漿區域420。在此揭露的實施例中，噴頭453比透孔456的最小直徑450 的長度還厚。為了維持受從腔室電漿區域420穿透至基材處理區域470的受激發物種具顯著濃度，可透過形成透孔456之較大的直徑部份使該較大的直徑部分穿過噴頭453達某一程度(part way)，而限制透孔最小直徑450的長度426。在所揭露的實施例中，透孔456的最小直徑450之長度可與透孔456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420中的電漿激發，噴頭453可(透過透孔456)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，透過第一通道412導入RPS410中及/或腔室電漿區域420中的製程氣體可含有氧(O2)、臭氧(O3)、N2O、NO、NO2、NH3、包括N2H4的NxHy、甲矽烷、乙矽烷、TSA及DSA之一者或多者。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413亦可傳遞製程氣體及/或載氣，及/或層固化氣體(例如O3)，該層固化氣體用於從生長中的層或剛沉積的層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456的數量可介於約60個至約2000個之間。透孔456可具有多種形狀，但最容易做成圓形。在所揭露的實施例中，透孔456的最小直徑450可介於 約0.5 mm至約20 mm之間，或介於約1 mm至約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470的小孔洞455數目可介於約100至約5000之間，或介於約500至約2000之間。小孔洞455的直徑可介於約0.1 mm至約2 mm之間。
第4B圖是根據所揭示的實施例與處理腔室一併使用的噴頭453之底視圖。噴頭453對應第4A圖中所圖示的噴頭。透孔456被繪成在噴頭453底部處具有較大的內徑(ID)，而在頂部處具有較小的ID。小孔洞455實質上在噴頭表面上均勻分佈，甚至分佈在透孔456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453中的透孔456抵達的電漿流出物與源自中空空間451穿過小孔洞455抵達的含矽前驅物結合時，在基材處理區域470內示範性的層建立在由底座(圖中未示)支撐的基材上。雖可將基材處理區域470裝配成支援電漿以供諸如固化之類的其他製程所用，然而在生長示範性層期間無電漿存在。
電漿既可在噴頭453上方的腔室電漿區域420中點燃，亦可在噴頭453下方的基材處理區域470點燃。電漿存在於腔室電漿區域420中，以從含氮與氫之氣體的流入中產生自由基氮前驅物。於處理腔室之蓋中形成的導電頂部部分421及噴頭453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420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470中的底部電漿或該底部電漿清潔接壤基材處理區域470的內部表面時，頂部電漿可處於低功率或無功率。透過在噴頭453及底座(或腔室底部)之間施加AC電壓，而點燃基材處理區域470中的電漿。清潔氣體可在電漿存在時導入基材處理區域470。
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℃)，此加熱是透過使用嵌入式單迴圈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。在一示範性實施例中，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)以及連結器規格與類型。VME標準亦界定匯流排結構為具有16位元資料匯流排或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，該等指令集指示時間、氣體混合、腔室壓力、腔室溫度、RF功率層級、基座位置及其他特殊製程參數。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層堆疊(例如依序沉積無碳的含矽氮與氫層而隨後沉積氧化矽覆蓋層)、將層轉換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，以操作程式中辨識的任務。
使用者與控制器之間的介面透過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。為了選擇特殊的螢幕或功能，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份，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 更多種氣體(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層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)在層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露之實施例的精神。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，應知亦具體揭露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以及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以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‧‧‧方法
202-212‧‧‧處理步驟
300‧‧‧處理系統
302‧‧‧FOUP
304、310‧‧‧機械手臂
306‧‧‧低壓固持區域
308a-f‧‧‧處理腔室
400‧‧‧基材處理腔室
410‧‧‧遠端電漿系統
411‧‧‧氣體入口組件
412、413‧‧‧通道
420‧‧‧腔室電漿區域
421‧‧‧蓋
424‧‧‧絕緣環
426‧‧‧長度
450‧‧‧直徑
451‧‧‧中空空間
453‧‧‧穿孔隔件
455‧‧‧小孔洞
456‧‧‧透孔
470‧‧‧基材處理區域
透過參考說明書之其餘部份及圖式，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，次符號與一元件符號相連且置於一破折號後，以標注類似部件之一者。當參考一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做介電層的所選擇的步驟。
第2圖是流程圖，說明用於根據本發明之實施例製做介電層的所選擇的步驟。
第3圖顯示根據本發明實施例的基材處理系統。
第4A圖顯示根據本發明實施例的基材處理腔室。
第4B圖顯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 (18)

  1. 一種在一基材上形成一介電層的方法，該方法包括下述依序的步驟：在含有該基材的一第一基材處理區域中，於該基材上形成一無碳的含矽氮與氫層，此步驟透過下述步驟完成：將一無激發的前驅物流進一遠端電漿區域以產生一自由基前驅物；在該第一基材處理區域中將一無碳的含矽前驅物與該自由基前驅物結合，其中在形成該無碳的含矽氮與氫層之操作期間該第一基材處理區域無電漿；以及沉積一無碳的含矽氮與氫層覆於該基材上，其中該無碳的含矽氮與氫層在沉積期間可流動；以及在該無碳的含矽氮與氫層上形成一氧化矽覆蓋層，此步驟透過下述步驟完成：將一含氧前驅物流進含有該基材的一第二基材處理區域；將一含矽前驅物流進該第二基材處理區域；在該第二基材處理區域中從該含氧前驅物與該含矽前驅物形成一電漿；以及沉積該氧化矽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，其中在形成該無碳的含矽氮與氫層期間，該基材的一溫度在約25℃以上至約125℃以下。
  3. 如請求項1所述之方法，進一步包含以下步驟：在一含氧氣氛中退火該介電層，以將該無碳的含矽氮與氫層轉換成一氧化矽層。
  4. 如請求項3所述之方法，其中該退火操作發生在形成該氧化矽覆蓋層之後。
  5. 如請求項3所述之方法，其中該退火操作發生在形成該無碳的含矽氮與氫層與形成該氧化矽覆蓋層之間。
  6. 如請求項1所述之方法，其中該基材溫度在形成該氧化矽覆蓋層期間為約200℃或更低。
  7. 如請求項1所述之方法，其中該氧化矽覆蓋層的一厚度為約10 nm或更大。
  8. 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。
  9. 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，且該無碳的含矽前驅物包含H2N(SiH3)、HN(SiH3)2、或N(SiH3)3之一者。
  10. 如請求項1所述之方法，其中該第一基材處理區域是該第二基材處理區域。
  11. 如請求項1所述之方法，其中在該第二基材處理區域中從該含氧前驅物與該含矽前驅物形成一電漿之步驟包含以下步驟：施加約1000 W或更低的一電漿功率。
  12. 一種在一基材上形成一介電層的方法，該方法包括下述依序的步驟：在含有該基材的一第一基材處理區域中，於該基材上形成一無碳的含矽氮與氫層，此步驟透過下述步驟完成：將一無激發的前驅物流進一遠端電漿區域以產生一自由基前驅物；在該第一基材處理區域中將一無碳的含矽前驅物與該自由基前驅物結合，其中在形成該無碳的含矽氮與氫層之操作期間該第一基材處理區域無 電漿；以及沉積一無碳的含矽氮與氫層覆於該基材上，其中該無碳的含矽氮與氫層在沉積期間可流動；以及處理該無碳的含矽氮與氫層，以將該無碳的含矽氮與氫層的一部分轉換成一氧化矽覆蓋層，此步驟透過下述步驟完成：將一含氧前驅物流進含有該基材的一第二基材處理區域；在該第二基材處理區域中從該含氧前驅物形成一電漿；以及將該無碳的含矽氮與氫層的一部分轉換成該氧化矽覆蓋層。
  13. 如請求項12所述之方法，其中在形成該無碳的含矽氮與氫層期間，該基材的一溫度在約25℃以上至約125℃以下。
  14. 如請求項12所述之方法，進一步包含以下步驟：在一含氧氣氛中退火該介電層，以將該無碳的含矽氮與氫層轉換成一氧化矽層。
  15. 如請求項14所述之方法，其中該固化[y3]操作發生在處理該無碳的含矽氮與氫層之後。
  16. 如請求項14所述之方法，其中該固化[y4]操作發生在形成該無碳的含矽氮與氫層與處理該無碳的含矽氮與氫層之間。
  17. 如請求項12所述之方法，其中該氧化矽覆蓋層的一厚度為約50 nm或更大。
  18. 如請求項12所述之方法，其中在該第二基材處理區域中從該含氧前驅物與該含矽前驅物形成一電漿之步驟包含以下步驟：施加約1000 W或更低的一電漿功率。
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