TW202106915A - 氮氧化物膜之形成方法 - Google Patents
氮氧化物膜之形成方法 Download PDFInfo
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- TW202106915A TW202106915A TW108141523A TW108141523A TW202106915A TW 202106915 A TW202106915 A TW 202106915A TW 108141523 A TW108141523 A TW 108141523A TW 108141523 A TW108141523 A TW 108141523A TW 202106915 A TW202106915 A TW 202106915A
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Abstract
一種併入氮之矽或金屬氧化物膜之形成方法,其包括(i)使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積矽或金屬氧化物膜,該電漿具有第一電漿密度;及(ii)使用氮化氣體而不使用任何前驅物,經由電漿氮化該矽或金屬氧化物膜,該電漿具有較第一電漿密度高之第二電漿密度。
Description
本發明大致係關於一種在半導體製程領域中形成氮氧化物膜之方法。
需要藉由電漿增強型原子層沉積法(PEALD)所沉積的高品質SiO膜,其具有諸如低濕式蝕刻速率及高耐受電壓之性質。習知用來沉積該等膜的常用方法係使用高RF功率及長的RF功率施加持續時間。然而,即使利用該方法,相對於熱氧化物膜之濕式蝕刻速率之膜的濕式蝕刻速率亦不低於大約2.0,且膜的崩潰電壓(以下稱為「Vbd」)不高於大約10 MV/cm。此外,在該方法之電漿條件下,下層膜或膜沉積基板被電漿氧化成為更明顯的問題。換言之,習知為形成具低濕式蝕刻速率及良好耐受電壓之SiO膜,提高用來產生電漿之RF功率,及/或使用諸如高於1,000°C之高溫(熱氧化物膜之高溫沉積可提供較佳膜品質)。然而,與PEALD相比,在埃等級的膜厚度控制困難,且亦存在因下層膜之熱降解而對製程溫度造成的限制。因此,希望在諸如500°C或更低之低溫下沉積膜,同時並提供良好的膜品質。作為另一方法,已有人報告利用PEALD經由交替沉積SiO膜及SiN膜而形成SiON膜之方法。然而,由於需要切換兩個製程(一個用來沉積SiO膜及另一個用來沉積SiN膜),因而此方法本質上具有製程複雜的問題。
關於相關技術之問題及解決方案的任何論述,僅出於提供本發明之背景脈絡而包括於本揭示案中,且不應被視為同意任何或全部該論述在進行本發明時為已知。
根據本發明之具體例,提供一種形成具有較習知SiO膜低之濕式蝕刻速率且具有良好耐受電壓之膜的方法。
在本揭示案中,SiO膜係經表徵或識別為氧化矽膜的膜,其可包括諸如氮、碳、氫等的其他元素及無可避免的雜質,其程度為該等元素不會實質地改變氧化矽膜的特性,及SiON膜係經表徵或識別為氮氧化矽膜的膜,其不為氧化矽膜亦不為氮化矽膜,且其可包括諸如碳、氫等的其他元素及無可避免的雜質,其程度為該等元素不會實質地改變氮氧化矽膜的特性;及類似地,SiN係經表徵或識別為氮化矽膜的膜,且其可包括諸如氧、碳、氫等的其他元素及無可避免的雜質,其程度為該等元素不會實質地改變氮化矽膜的特性,其中除非另外說明,否則膜的名稱,諸如SiO膜、SiON膜、及SiN膜,係僅以非化學計量方式指示膜類型的簡寫(單單藉由主要組成元素來指示)。
為解決習知方法中的至少一個問題,本發明人已發展出可經由將氮併入至於例示性具體例中藉由PEALD沉積之SiO膜中來達成SiO膜之低濕式蝕刻速率的技術。在本揭示案中,在例示性具體例中,術語「併入氮」係指經由通過取代反應用Si-N鍵置換一些Si-O鍵來將氮引入至SiO膜中由Si-O鍵所構成之分子結構中,藉此產生SiON膜。在替代具體例中,將氧併入至SiN膜中,及術語「併入氧」係指經由通過取代反應用Si-O鍵置換一些Si-N鍵來將氧引入至SiN膜中由Si-N鍵所構成之分子結構中,藉此產生SiNO膜。
在一些具體例中,經由使用較習用之RF功率低的RF功率,例如,低於300 W及/或使用較習用之製程溫度低之製程溫度,例如,低於500°C,沉積膜以抑制下層膜之氧化,及經由在沉積膜之前、之中、及/或之後進行特定處理,可形成具高膜品質的膜。在本揭示案中,除非另外明確說明,否則任何指示的RF功率係針對300 mm晶圓,且可經轉換成W/cm2
(每單位晶圓面積之瓦數),其可適用於具有不同直徑(諸如200 mm或450 mm)之晶圓。
在一些具體例中,膜形成方法包括沉積SiO膜之步驟,其包含使用氧源(例如,BDEAS (雙(二乙胺基)矽烷)作為單一前驅物或前驅物之單一組合的沉積循環,及用來氮化SiO膜之電漿處理步驟,其中可經由操控處理條件及處理序列來達成所得膜中的高膜品質。由於僅使用單一前驅物或前驅物之單一組合來形成SiON膜,而未切換SiO膜形成序列及SiN膜形成序列,因而可以高生產力及高穩定性製得SiON膜。此外,由於設備僅使用一個瓶子來儲存前驅物(當使用單一前驅物時),因而設備可廉價地提供且可以高操作速率操作。
為了概述本發明之態樣及相對於相關技術所達成之優點,在本揭示中描述本發明之某些目的及優點。當然,應了解的是,可無須根據本發明之任何特定具體例來達成所有此類目標或優點。因此,舉例而言,熟悉本技藝者將認知到,可以達成或最佳化如本文中所教示之一個優點或一組優點而無須達成本文中可能教示或建議之其他目的或優點的方式來實踐或進行本發明。
本發明之其他態樣、特徵及優點將由隨後之詳細描述而變得顯而易見。
具體例之詳細說明
在本揭示中,「氣體」可包括汽化之固體及/或液體且可由單一氣體或氣體混合物構成。在本揭示中,經由噴淋頭引入至反應室之製程氣體可包含前驅物氣體及添加劑氣體、基本上由前驅物氣體及添加劑氣體組成或由前驅物氣體及添加劑氣體組成。前驅物氣體及添加劑氣體通常係作為混合氣體或個別地引入至反應空間。前驅物氣體可利用載送氣體(諸如稀有氣體)引入。添加劑氣體可包含反應物氣體及稀釋氣體(諸如稀有氣體)、基本上由反應物氣體及稀釋氣體(諸如稀有氣體)組成或由反應物氣體及稀釋氣體(諸如稀有氣體)組成。反應物氣體包括氧化氣體(例如,含氧氣體或氧源氣體)及氮化氣體(例如,含氮氣體或氮源氣體)。反應物氣體及稀釋氣體可作為混合氣體或個別地引入至反應空間。前驅物可包含兩種或更多種前驅物,且反應物氣體可包含兩種或更多種反應物氣體。前驅物係可化學吸附於基板上的氣體且通常含有構成介電膜之基質之主要結構的類金屬或金屬元素,而用於沉積的反應物氣體係當氣體經激發以將原子層或單層固定於基板上時可與化學吸附於基板上之前驅物反應的氣體,或可與單層或堆疊的多個單層反應以處理該等層的氣體。「化學吸附」係指化學飽和吸附。可使用除製程氣體外之氣體(即,非通過噴淋頭引入之氣體)來(例如)密封反應空間,該氣體包括諸如稀有氣體之密封氣體。在一些具體例中,「膜」係指用以覆蓋整個目標或所關注表面,實質上無針孔地在垂直於厚度方向之方向上連續地延伸之層,或簡單地,覆蓋目標或所關注表面之層。在一些具體例中,「層」係指形成於表面上的具有特定厚度之結構或膜或非膜結構之同義詞。膜或層可由具有特定特徵之離散單一膜或層或者多個膜或層構成,且相鄰膜或層之間的邊界可為或可不為明顯的且可基於相鄰膜或層之物理、化學及/或任何其他特徵、形成製程或序列及/或功能或用途而建立。
此外,在本揭示中,除非另外指明,否則冠詞「一」係指一個物種或包括多個物種之屬。在一些具體例中,術語「由……構成」及「具有」獨立地指「通常或廣泛地包含」、「包含」、「基本上由……組成」或「由……組成」。此外,在本揭示中,在一些具體例中,任何已定義之意義未必排除一般及慣用意義。
此外,在本揭示中,變數之任何兩個數目可構成變數之可工作範圍,此係因為可工作範圍可基於例行工作而判定,且所指示之任何範圍可包括或排除端點。另外,所指示的變數之任何數值(不管該等數值是否用「約」來指示)可意指精確值或近似值且包括等效值,且在一些具體例中可意指平均值、中值、代表值、多數值等。
在本揭示案中條件及/或結構未得到具體規定之處,熟悉本技藝者可鑒於本揭示案容易地提供此類條件及/或結構,作為常規實驗內容。在所有已揭示具體例中,於一具體例所使用之任何元件可由與其等效的任何元件替換,包括用於預期目的而在本文中明確地、必須地或固有地揭示之彼等元件。此外,本發明同樣可適用於設備及方法。
將針對各種態樣中之較佳具體例來解說該等具體例。然而,本發明並非侷限於該等較佳具體例。
一些具體例係針對一種併入氮之矽或金屬氧化物膜之形成方法,其包括以下步驟:(i)使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積矽或金屬氧化物膜,該電漿具有第一電漿密度;及(ii)使用氮化氣體而不使用任何前驅物(不沉積膜),經由電漿氮化(併入氮至)矽或金屬氧化物膜,該電漿具有較第一電漿密度高之第二電漿密度。在一些具體例中,第二電漿密度較第一電漿密度高1.1倍至3倍(例如,1.3倍至2倍)。
在一些具體例中,併入氮之矽或金屬氧化物膜係指使用相同前驅物沉積之整體矽或金屬氧化物膜,其之至少部分轉變為由併入氮之矽或金屬氧化物所構成的矽或金屬氮氧化物(其表示為SiON或MON),其中氮之含量為至少1原子%但小於氧之含量,例如,在2原子%至30原子%之範圍內,通常5原子%至20原子%,例如大約10原子%(±3原子%)。舉例來說,底部層(或界面層)、頂部層、及/或介於底部與頂部層之間的至少一層係由SiON或MON所構成。在一些具體例中,整個矽或金屬氧化物膜係由SiON或MON所構成。
電漿係具高自由電子含量(約50%)的部分游離氣體。電漿之轟擊可以電漿密度或離子的動能來表示。電漿密度亦稱為「電子密度」或「離子飽和電流密度」且係指每單位體積之自由電子的數目。反應空間中之電漿密度可使用蘭牟而(Langmuir)探針(例如,LMP系列)來測量且可使用探針方法(例如,「使用混成蘭牟而探針及微波干涉儀方法的高準確度電漿密度測量」,Deline C等人, Rev. Sci. Instrum. 2007年11月;78(11): 113504,將其揭示內容之全體以引用的方式併入本文)來測定。電漿密度主要可藉由調整壓力及RF功率來調節(壓力愈低及功率愈高,電漿密度就變得愈高)。電漿密度亦可藉由施加具有針對隨後離子設定之較低頻率(<1MHz)之DC偏電壓或AC電壓來調節。如使用電漿產生氣體用來產生電漿之條件(其中不將前驅物及反應物列入考慮),諸如除RF功率外之溫度及壓力及電漿產生氣體之類型,於步驟(i)及步驟(ii)中實質上相同,則當判定何種電漿具有較另一者高之電漿密度時,電漿密度可由施加至電漿產生氣體之RF功率來表示。
在一些具體例中,電漿係電容耦合電漿(CCP)。然而,替代地或另外地,可使用遠端電漿或其他電漿諸如感應耦合電漿(ICP)、電子迴旋加速器諧振電漿(ECP)、及螺旋錐波電漿(HWP),當氮源氣體暴露至電漿時,其可產生,例如,氮自由基及氮離子。如諸如上述之電漿類型在沉積步驟與氮化步驟之間不同,則可針對各別步驟使用不同的反應室。例示性的電漿產生氣體係諸如Ar、He、Kr、及其任何組合的稀有氣體。
關於含有矽或金屬(例如,Mg、Al、Si、Ti、Ge、Zr、Ru、Hf、或Ta)之前驅物,可使用任何能夠形成氧化物膜的前驅物。舉例來說,可單獨或以下述兩者或更多者之任何組合有利地使用有機胺基矽烷諸如BDEAS (雙-二乙胺基矽烷)、3DMAS (叁(二甲胺基)矽烷)、或其類似物,金屬鹵化物諸如TiCl4,金屬醯胺諸如TDMAT(肆(二甲胺基)鈦)及TDMAGe(肆(二甲胺基)鍺烷)、或金屬有機化合物諸如Ru(EtCp)2(雙(乙基環戊二烯基)釕)。Ar、He、或其類似物可單獨或以前述中兩者或更多者之任何組合有利地使用作為載送氣體及稀釋氣體中之各者。在一些具體例中,載送氣體係在整個步驟(i)(及此外在一些具體例中在整個步驟(ii))連續地饋送至反應空間。在一些具體例中,在電漿增強型原子層沉積(PEALD)中,前驅物饋送循環之持續時間係在0.1秒至2.0秒之範圍內,例如,0.5秒至1.0秒。
在一些具體例中,該方法進一步包括,在步驟(i)之前,(ii’)使用氮化氣體而不使用任何前驅物,經由電漿氮化基板之表面。以上,如基板界面係由矽構成,則表面成為氮化矽,於其上在步驟(i)中沉積SiO膜,隨後為步驟(ii)氮化SiO膜,其中可形成Si/SiON/SiO/SiON 之層結構。當少量氮存在於基板界面上時(輕度界面氮化),可改良膜之電特性,及此外,可改良SiO膜之黏著。
在一些具體例中,可以如下方式來控制步驟 (ii’)及步驟 (ii)之氮化的時序及/或重複頻率:在步驟(i)期間之任何給定點在基板界面上(即在SiO膜中之厚度方向中的任何給定位置,例如,在SiO膜的任何單層之間)、及/或在SiO膜之頂部上進行氮化,此外,可控制併入SiO膜中之氮的量,藉此視需要調整層結構,而無製程之複雜性。為實現以上具體例,在一些具體例中所提供一種併入氮之矽或金屬氧化物膜之形成方法係經由在期望位置將矽或金屬氧化物膜轉變為矽或金屬氮氧化物膜,其包括以下步驟:(a)設計併入氮之矽或金屬氧化物膜之層結構,該層結構係由以矽或金屬氧化物膜組成之層A及以矽或金屬氮氧化物膜組成之層B所構成;(b)根據該設計,關於層A,使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積矽或金屬氧化物膜,該電漿具有第一電漿密度;及(c)根據該設計,關於層B,使用氮化氣體而不使用任何前驅物,經由電漿以將矽或金屬氧化物膜轉變為矽或金屬氮氧化物膜之方式氮化矽或金屬氧化物膜,該電漿具有較第一電漿密度高之第二電漿密度。在一些具體例中,併入氮之矽或金屬氧化物膜係由交替層疊之層A的多個層及層B的多個層所構成。在一些具體例中,層A之總厚度對層B之總厚度的比係0/100至99/1 (例如,20/80、30/70、40/50、50/50、及介於其間的任何比)。在一些具體例中,層B(SiON之層)的厚度係 0.1 nm至2 nm,例如大約1 nm。因此,例如,經由於步驟(b)中每次沉積具有大約1 nm之厚度的SiO膜後進行步驟(c)之氮化,可形成完全由SiON所構成的層結構。或者,例如,經由於步驟(b)中每次沉積具有大約2 nm之厚度的SiO膜後進行步驟(c)之氮化,層結構係由SiO層及SiON層構成之條紋圖案所構成,而無製程之複雜性。在一些具體例中,取決於目標層結構,於步驟(b)中之每1至100個循環(例如,2至30個循環)之PEALD後重複進行步驟(c)。
在一些具體例中,在步驟(i)中,藉由PEALD沉積矽或金屬氧化物膜。因此,可於基板之圖案化凹槽或階梯(例如,溝槽)中沉積保形SiO膜。相同的結構可被稱為凹槽以及階梯,其中參照頂部表面該結構係為凹槽而參照底部表面該結構係為階梯。在本揭示案中,溝槽、通孔及任何其他凹槽稱為「凹槽」。在一些具體例中,圖案係由凹槽或階梯構成。在一些具體例中,凹槽之寬度為10至50 nm (通常為15至30 nm),深度為30至200 nm (通常50至150 nm),且縱橫比為3至20 (通常為3至10)。在一些具體例中,氧化物膜具有80%至100%(通常約90%或更高)的保形性,其中「保形性」藉由比較在凹槽的側壁或底部上之某一點(通常為中間點)所沉積之膜厚與正好在凹槽外的平坦表面上所沉積之膜厚來判定。
在一些具體例中,在PEALD中,氧化氣體包含氧及氮兩者,及例示性的氧化氣體包括,但不限於,N2
O、NO、NH3
+O2
、及N2
+O2
。或者,在一些具體例中,在PEALD中,氧化氣體包含不含氮的氧,及例示性的氧化氣體包括,但不限於,O2
、O3
、及其類似物。
在一些具體例中,在PEALD中,在步驟(i)中,電漿係經由向電極施加RF功率所產生之電容耦合電漿(CCP),其中在PEALD之各循環中RF功率之持續時間係2.0秒或以下(例如,0.1秒至1.5秒,或0.5秒至1.2秒)及RF功率之功率係每cm2
之基板表面0.28 W或以下,即就300-mm基板而言為200 W或以下(例如,35 W至150 W、或50 W至100 W),例如(可將RF功率(W/cm2
)應用至除300-mm基板外之基板)。經由使用相當低的RF功率,可沉積SiO膜而不氧化下層膜(例如,先前於步驟(ii)中氮化之下層SiON膜),及另外地,SiO膜可具有相當容易被氮化的特性(即氮相當易併入至SiO膜中),其可歸因於,例如,SiO膜之相當低的緻密化。基於類似原因,在一些具體例中,施加RF功率之脈衝具有2.0秒或以下(例如,0.3至1.0秒、或0.1至0.5秒)的持續時間。在一些具體例中,RF功率係為200 kHz至600 MHz,例如13.56 MHz。在一些具體例中,可使用感應耦合電漿(ICP)或遠端電漿(PR)來替代CCP。
在一些具體例中,步驟(ii)中之製程溫度係在50°C至500°C之範圍內,例如,300°C至400°C;步驟(ii)中之製程壓力係在200 Pa至2000 Pa之範圍內,例如,300 Pa至400 Pa;步驟(i)中之製程溫度係在50°C至500°C之範圍內,例如,300°C至400°C;及步驟(i)中之製程壓力係在200 Pa至2000 Pa之範圍內,例如,300 Pa至400 Pa。
在一些具體例中,在步驟(i)中,氧化氣體之流動速率係在500 sccm至4,000 sccm之範圍內,例如,1,000 sccm至3,000 sccm;及載送氣體之流動速率係在500 sccm至4,000 sccm之範圍內,例如約2,000 sccm。
在一些具體例中,在步驟(ii)中,電漿係經由向電極施加RF功率所產生,其中RF功率之功率係每cm2
之基板表面0.42 W或以上,即就300-mm基板而言為300 W或以上(例如,300 W至400 W),例如,以致可有效地完成SiO膜的氮化。在一些具體例中,步驟(ii)中所使用之RF功率係連續的,或者間歇的(脈衝式)。在一些具體例中,步驟(ii)中之RF功率係200 kHz至600 MHz,例如13.56 MHz,其與步驟(i)中相同。
在一些具體例中,步驟(i)及步驟(ii)係於相同反應空間或不同反應空間中進行,在步驟(i)及(ii)中向該(等)反應空間供應惰性氣體,使得步驟(i)及步驟(ii)可以高生產力連續地進行,且於步驟(i)及步驟(ii)之間沒有不期望的顆粒污染或當暴露至空氣時沒有不期望的氧化。惰性氣體於步驟(i)及(ii)中作為電漿產生氣體,及於步驟(ii)中,不僅用來氮化氧化物膜,而且用來將氮有效地併入至氧化物膜中,以將氧化物膜轉變為併入氮之氧化物膜,使用惰性氣體有效地在暴露至惰性氣體之電漿時使氮離子更容易地自氮化氣體解離。在一些具體例中,在步驟(ii)中,氮化氣體對惰性氣體之流量比為1/99或以上,例如,10/90至50/50。氮化氣體對惰性氣體之流量比係控制氮游離容易度的參數。在一些具體例中,氮化氣體係N2
、NH3
、或N2
+H2
。在一些具體例中,氮化氣體之流動速率係在500 sccm至4,000 sccm之範圍內,例如,1,000 sccm至3,000 sccm;及惰性氣體(諸如稀有氣體)之流動速率係在500 sccm至4,000 sccm之範圍內,例如約2,000 sccm。
在一些具體例中,步驟(ii)中之製程溫度係在50°C至500°C之範圍內,例如,300°C至400°C;步驟(ii)中之製程壓力係在200 Pa至2000 Pa之範圍內,例如,300 Pa至400 Pa;及步驟(ii)之持續時間係在60秒至600秒之範圍內,例如,60秒至180秒。在一些具體例中,在步驟(i)及(ii)中,製程溫度及製程壓力係以相同方式控制。
在一些具體例中,根據前述相同原理,亦可將除氮之外的元素,諸如B、C、Al、P、S、Ga、及As,併入至矽或金屬氧化物膜中,該等具體例包括一種併入元素X之矽或金屬氧化物膜之形成方法,其包括以下步驟:(i)使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積矽或金屬氧化物膜,該電漿具有第一電漿密度;及(ii)不使用任何用來沉積之前驅物,經由電漿激發含有元素X之氣體及將元素X併入至矽或金屬氧化物膜中,該電漿具有較第一電漿密度高之第二電漿密度。由於元素X可以與併入氮的類似方式併入,因此熟悉技藝人士可鑑於本揭示,根據例行實驗輕易地提供未明確說明於文中的條件及/或結構。
在本發明之另一態樣中,一些具體例提供一種併入氧之矽或金屬氮化物膜之形成方法,其包括以下步驟:(I)使用含有矽或金屬之前驅物及氮化氣體,經由電漿於基板上沉積矽或金屬氮化物膜,該電漿具有第一電漿密度;及(II)使用氧化氣體而不使用任何前驅物,經由電漿氧化矽或金屬氮化物膜,該電漿具有較第一電漿密度低之第二電漿密度。形成併入氧之矽或金屬氮化物膜來替代本揭示中描述之併入氮之矽或金屬氧化物膜可以與後者實質上類似的方式進行,熟悉技藝人士可鑑於本揭示,根據例行實驗輕易地提供用來進行前者的條件及/或結構。
將參照圖式中顯示的具體例來詳細說明本發明。然而,該等具體例並不意欲限制本發明。
圖7繪示根據一具體例之併入氮之氧化矽膜之形成的示意性製程序列,其中各欄的寬度不一定代表實際的時間長度,且各列中線的高起水平代表開-狀態,而各列中線的底部水平代表關-狀態。在此具體例中,氧化物膜沉積步驟及氮化步驟係於PEALD設備的相同反應室中進行。所繪示的氧化物膜沉積步驟顯示PEALD的一個循環,其大體上對應於形成一單層,且在移至氮化步驟之前可重複該循環直至獲得期望膜厚度。在此具體例中,載送氣體及稀釋氣體係在整個氧化物膜沉積步驟及氮化步驟中連續地饋送至反應空間。氧化氣體僅在整個步驟(i)連續地饋送至反應空間,而氮源氣體僅在整個步驟(ii)連續地饋送至反應空間,其中在氧化物膜沉積步驟與氮化步驟之間的過渡期間(氣體變換步驟),氧化氣體之流量減小至零,而氮源氣體之流量自零增加。在每個沉積循環中,前驅物僅以一脈衝饋送,隨後為施加RF功率之脈衝。在此具體例中,載送氣體及/或稀釋氣體亦作為電漿產生氣體及清除氣體。在氮化步驟中,RF功率係在未饋送任何前驅物的情況下施加。
在此具體例中,氧化物膜沉積步驟及氮化步驟係於相同反應室中進行;然而,此等步驟可於不同反應室中連續進行,此外,不管是否使用相同反應室或不同反應室,電漿產生氣體(例如,稀有氣體)在氧化物膜沉積步驟及氮化步驟中可相同或不同。舉例來說,在氧化物膜沉積步驟中,使用Ar,而在氮化步驟中,使用He作為電漿產生氣體。
圖8顯示根據本發明之一具體例之沉積氧化矽膜之示意性製程序列與氮化氧化矽膜之示意性製程序列的組合,其中灰色格子表示「開」狀態(深灰色代表較高強度),而白色格子表示「關」狀態,且每一欄之寬度不表示各製程之持續時間。此示意性製程序列係對應於圖7中所繪示者。在此具體例中,氧化物膜沉積步驟係PEALD之一步驟,其包含「穩定」(穩定化),其中將載送氣體/稀釋氣體及氧化氣體饋送至反應空間來穩定反應空間中之氣體流量;「饋送」(0.1至1.0秒,較佳0.2至0.5秒),其中前驅物在饋送載送氣體/稀釋氣體及氧化氣體的同時饋送至反應空間用來將前驅物吸附於基板表面上;「清除」(0.1至2.0秒,較佳0.3至1.5秒),其中載送氣體/稀釋氣體及氧化氣體連續地饋送至反應空間而未饋送前驅物,用來移除未經吸附之前驅物及清除反應空間;「沉積」(0.1至2.0秒,較佳0.3至1.5秒),其中在連續饋送載送氣體/稀釋氣體及氧化氣體但不饋送前驅物的同時向反應空間施加RF功率,以於基板之經前驅物吸附之表面上引起電漿反應從而形成單層;及「清除」(0.05至1.0秒,較佳0.1至0.5秒),其中將載送氣體/稀釋氣體及氧化氣體連續地饋送至反應空間但不饋送前驅物,用來移除未反應組分及副產物及清除反應空間。以上構成PEALD的一個循環,且該循環根據用來氮化的目標厚度進行一次或重複數百次。
在以上描述的製程序列中,前驅物係使用連續供應的載送氣體於一脈衝中供應。此操作可使用流通系統(FPS)來實現,其中載送氣體管線具備具有前驅物儲槽(瓶)之歧路管線,且主管線及歧路管線經切換,其中當僅意欲將載送氣體饋送至反應室時,關閉歧路管線,而當意欲將載送氣體及前驅物氣體兩者饋送至反應室時,主管線關閉且載送氣體流過歧路管線且與前驅物氣體一起自瓶流出。以此方式,載送氣體可連續地流至反應室中,且可藉由切換主管線及歧路管線而以脈衝方式載送前驅物氣體。圖1B繪示根據本發明一個具體例的使用流通系統(FPS)之前驅物供應系統(黑色閥指示該等閥關閉)。如圖1B中之(a)所示,當將前驅物饋送至反應室(未圖示)時,首先,諸如Ar (或He)之載送氣體流過具有閥b及c之氣體管線,且接著進入瓶(儲槽) 30。載送氣體自瓶30流出,同時載送對應於瓶30內蒸氣壓力之量的前驅物氣體,且流過具有閥f及e之氣體管線,且接著與前驅物一起饋送至反應室。在上文中,閥a及d關閉。當僅將載送氣體(稀有氣體)饋送至反應室時,如圖1B中之(b)所示,載送氣體流過具有閥a之氣體管線,同時繞過瓶30。在上文中,閥b、c、d、e及f關閉。
於氧化物膜沉積步驟完成後,「氣體流動」步驟開始轉變反應空間中之氣體用於氮化,其中將載送氣體/稀釋氣體連續饋送至反應空間,而將氧化氣體逐漸調降至零,同時使氮源氣體開始流動且以經由使氧化氣體之減小及氮化氣體之增加平衡以實質上維持反應空間中壓力的方式逐漸提高其流量。於「氣體流動」後,開始氮化步驟,其包含「穩定」(穩定化),其中將載送氣體/稀釋氣體及氮化氣體饋送至反應空間用來穩定反應空間中之氣體流量;「處理」,其中在連續饋送載送氣體/稀釋氣體及氮化氣體但不饋送任何前驅物的同時向反應空間施加RF功率,以將氮自氧化物膜之暴露表面併入至氧化物膜中;及「清除」,其中將載送氣體/稀釋氣體及氮化氣體連續地饋送至反應空間但不饋送任何前驅物,用來移除未反應組分及副產物及清除反應空間。於氧化物膜沉積步驟中之每一個或數百個循環後進行此步驟一次,及根據目標層狀結構及所得併入氮之氧化物膜之目標厚度將氧化物膜沉積步驟及氮化步驟進行一次或重複數十次。為有效地抑制氧化物膜沉積步驟中之下層之氧化,及為將氮有效地併入至氧化物膜中,氮化步驟中之RF功率(電漿密度)較於氧化物膜沉積步驟中高。氧化物膜沉積步驟中之RF功率較於氮化步驟中低,其之程度為所得氧化物膜之濕式蝕刻速率較熱氧化物膜之濕式蝕刻速率高大約至少2.5倍(例如,3或4倍),即RF功率相當低以致氧化物膜的緻密化不完全。
圖9係說明根據本發明之一具體例形成具有期望層結構之併入氮之氧化矽膜之步驟的流程圖。在步驟S1中,設計由氧化矽(SiO)層及氮氧化矽(SiON)層所構成之目標層結構,其中,例如,底部層(或界面層)、頂部層、及/或介於底部與頂部層之間的至少一個層係由SiON所構成。在一些具體例中,形成由於厚度方向中交替堆疊之SiO層及SiON層所構成的條紋圖案。在一些具體例中,整個氧化矽膜係由SiON所構成。在步驟S1中,可設計諸如圖17中所繪示的層結構。
圖17示意性地繪示根據本發明之具體例由SiO層及SiON層構成的層狀結構,其中在(a)中SiON層構成最上層,在(b)中SiON層及SiO層於厚度方向中交替堆疊,及在(c)中SiON層構成底部層(其可稱為介於Si基板與併入氮之氧化矽膜之間的界面層)。在(b)中,SiO及SiON層之各厚度可經由改變每個處理(步驟S4)之SiO沉積循環(步驟S3)的數目來調整。
根據於步驟S1中確定的目標層結構,如底部層(或界面層)欲由SiON構成(當下層係矽基板時),則進行步驟S2,其中於氧化物膜沉積步驟(步驟S3)之前,進行氮化步驟以氮化下層(矽基板)而形成界面層(底部層),該層由於當進行下一步驟S3時之氧化結果而成為SiON。在步驟S3中,氧化物膜沉積步驟係經由PEALD進行,其中進行一至數百個沉積循環,及於步驟S3後,進行氮化步驟(步驟S4)。步驟S4係於步驟S3之後進行一次。其後,根據於步驟S1中確定的目標層結構,於步驟S5中重複步驟S3及S4。步驟S3及S4係進行一次或更多次(例如,數十次)。
在一些具體例中,氧化矽膜之沉積循環係經由PEALD在以下明確說明的條件下進行:
A)氧化氣體包含氮諸如 N2
O、NO、NH3
+O2
、及/或N2
+O2 。
在一些具體例中,氧化氣體包含不含氮的氧諸如O2
。
B)用於前驅物的載送氣體係惰性氣體諸如Ar、He、Kr、及/或N2
。
C)用來沉積SiO層之電漿脈衝的持續時間係短至2.0秒或以下。
D)用來沉積SiO層之RF功率係低至200 W或以下(就300-mm晶圓而言)。
在一些具體例中,氧化矽膜之氮化係在以下明確說明的條件下進行。
E)氮化係於沉積步驟之前、之中、及/或之後進行。
F)使用含氮氣體諸如N2
、NH3
、及/或N2
+H2
。
G)含氮氣體係經由將其與Ar、He、或Ar及He之組合混合來使用。
H)含氮氣體對混合氣體之流量比係1/100至50/100(1%至50%)。
I)用來氮化之RF功率係至少300 W(就300-mm晶圓而言)。
J)不使用前驅物。
用於沉積之電漿可於原位產生,例如,於在整個沉積循環中連續流動之惰性氣體氛圍中。在其他具體例中,電漿可於遠端產生且提供至反應室。當使用遠端電漿替代直接電漿(例如,CCP)時,遠端電漿單元可使用30W至8 kW之功率來進行氮化步驟。
可使用例如包括圖1A中所繪示之設備的任何適合之設備來執行製程循環。圖1A為氣體脈衝PECVD設備之示意圖,其期望地結合可經程式化以進行下文所描述之序列的控制,可用於本發明之一些具體例中。在此圖中,藉由在反應室3之內部11 (反應區)中設置彼此平行且面對的一對導電之平板電極4、2,向一側施加HRF功率(13.56 MHz或27 MHz) 20且將另一側12電接地,在該等電極之間激發電漿。溫度調節器設置在下台(lower stage) 2 (下部電極)中,且置放在其上之基板1的溫度在給定溫度下保持恆定。上部電極4亦充當噴淋板,且反應氣體(及稀有氣體)及前驅物氣體分別經由氣體管線21及氣體管線22及經由噴淋板4而引入至反應室3中。另外,在反應室3中,設置具有排氣管線7之圓管13,經由所述排氣管線將反應室3之內部11中的氣體排出。另外,稀釋氣體經由氣體管線23而引入至反應室3中。此外,安置於反應室3下方之轉移室5具備密封氣體管線24以經由轉移室5之內部16 (轉移區)將密封氣體引入至反應室3之內部11中,其中設置有用於將反應區與轉移區隔開之分隔板14 (自此圖省略閘閥,晶圓經由該閘閥轉移至轉移室5中或自該轉移室轉移)。轉移室亦具有排氣管線6。在一些具體例中,多元素膜沉積及表面處理在同一反應空間中執行,以使得所有步驟可連續進行,而不會將基板暴露於空氣或其他含氧氛圍中。在一些具體例中,遠端電漿單元可用於激發氣體。
熟悉本技藝者應瞭解,設備包括一個或多個控制器(未顯示),其經程式化或另外構造以導致進行本文中別處所描述之沉積及反應器清潔製程。如熟悉本技藝者應瞭解,控制器係與反應器之各種電源、加熱系統、泵、機器人系統及氣流控制器或閥通信。
在一些具體例中,在圖1A中所描繪之設備中,可使用圖1B中所繪示的切換不活性氣體之流動與前驅物氣體之流動的系統(先前描述)來以脈衝形式引入前驅物氣體,而不使反應室壓力出現實質波動。
在一些具體例中,可使用雙腔室反應器(彼此緊密安置的兩個用於加工晶圓之區段或隔室),其中反應物氣體及稀有氣體可經由共用管線來供應,而前驅物氣體係經由非共用管線來供應。
在一些具體例中,不僅可調整於氧化物膜中併入氮的位置,而且亦可調整氮的併入量。氮的併入量可經由調整,例如,氮化步驟的持續時間、施加至反應空間之RF功率、饋送至反應空間之氮源氣體中之氮濃度、及/或氮化步驟期間於反應空間中之製程壓力來調整。
在本發明之另一態樣中,該技術可應用於矽或金屬氮化物膜且可將氧併入至矽/金屬氮化物膜中。在一些具體例中,氮化矽膜之沉積循環係經由PEALD在以下明確說明的條件下進行:
A)使用諸如N2
、NH3
、及/或N2
+H2
的含氮氣體。
B)用於前驅物的載送氣體係惰性氣體諸如Ar、He、Kr、及/或N2
。
C)用來沉積SiN層之RF功率係至少100 W(就300-mm晶圓而言)。
在一些具體例中,氮化矽膜之氧化係在以下明確說明的條件下進行。
D)氧化係於沉積步驟之前、之中、及/或之後進行。
E)氧化氣體包含氮諸如N2
O、NO、NH3
+O2
、及/或N2
+O2 。
在一些具體例中,氧化氣體包含不含氮的氧諸如O2
。
F)氧化氣體係經由將其與Ar、He、Kr、及/或N2
混合來使用。
G)氧化氣體對混合氣體之流量比係1/100至50/100(1%至50%)。
H)用來處理SiN層之電漿脈衝的持續時間係短至2.0秒或以下。
I)用來氧化之RF功率係200 W或以下(就300-mm晶圓而言)。
J)不使用前驅物。
本發明將參考下文工作實施例來進行進一步解釋。然而,該等實施例並不意欲限制本發明。在未明確說明條件及/或結構之實施例中,熟悉本技藝者可鑒於本揭示,根據例行實驗容易地提供此類條件及/或結構。此外,在一些具體例中,特定實施例中所應用之數字可在至少±50%之範圍內進行修改,且該等數字為近似值。
實施例
參考例
1
利用PEALD在說明於下之條件下使用圖1A及1B中繪示之PEALD設備基於圖7中繪示為「氧化物膜沉積步驟」之序列(沒有「氮化步驟」)經由改變RF功率來各自於Si基板 (Ф300 mm)上沉積SiO膜。
沉積條件:RF開時間:1.0秒;RF功率(13.56 MHz):變化,見圖2;壓力:333 Pa;基座溫度:390°C;前驅物:BDEAS;載送氣體:He (2.15 slm);稀釋氣體:He (1.05 slm);氧化氣體(反應物):N2
O (0.8 slm);循環數目:600(所得膜之厚度:40 nm)。
於將各基板自反應室取出後,使用DHF (100:1)持續1分鐘來測量各膜的濕式蝕刻速率。圖2係顯示氧化矽膜之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WER Tox 比」)、及用於沉積氧化矽膜之RF功率(高頻)(「HRF」)之間的關係圖。如可自圖2所見,當RF功率為500 W或更高時,氧化矽膜之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WERR」)為約2.0,而當RF功率為200 W或以下時,WERR為約4.0或更高。此顯示當RF功率為200 W或以下時,雖然可抑制下層之氧化,但氧化矽膜之WERR變得過高,即膜品質變得不令人滿意。
比較例
1
除了RF功率為100 W外,以與參考例1相同之方式利用PEALD將SiO膜沉積於具有深度100 nm、寬度30 nm、及間距45 nm之溝槽的Si基板(Ф300 mm)上。
於將各基板自反應室取出後,使用DHF (200:1)持續1分鐘來進行濕式蝕刻。圖3顯示橫截面圖的STEM (掃描穿透式電子顯微鏡)照片,其顯示剛沉積於溝槽中之氧化矽膜(「剛沉積」)及顯示重疊於照片上、封於方框中之於濕式蝕刻後的氧化矽膜(「於濕式蝕刻後」)。如可由圖3所見,雖然當沉積氧化矽膜時,其保形性高(約98%),但於濕式蝕刻後,沉積於溝槽側壁上之部分的膜幾乎完全被移除。此意謂儘管沉積於頂表面上之部分的膜可能具有良好的WERR,但沉積於溝槽側壁上之部分的膜具有相當高的WERR。此係習知氧化矽膜的第二個問題(第一個問題係下層的氧化)。
實施例
1
及比較例
2
在實施例1中,利用PEALD在下表1中指示之條件下使用圖1A及1B中繪示之PEALD設備基於圖8及9中繪示之序列在Si基板(Ф300 mm)上形成併入氮之SiO膜。
表1 (數字為近似值)
參數 | ||
沉積循環(PEALD) | 基板溫度 | 300°C |
壓力 | 400 Pa | |
前驅物脈衝 | 0.5 秒 (BDEAS) | |
氧化氣體之流動速率(連續) | 0.8 slm (N2 O) | |
載送氣體之流動速率(連續) | 1.5 slm (He) | |
稀釋氣體之流動速率(連續) | 0.7 slm (He) | |
RF功率(13.56 MHz) | 100 W | |
RF功率脈衝 | 1.5秒 | |
循環數目 | 30個循環 | |
氧化物膜的厚度 | 約33 nm | |
氮化處理 | 基板溫度 | 300°C |
壓力 | 400 Pa | |
氮源氣體之流動速率(連續) | 0.8 slm (N2 ) | |
稀釋氣體之總流動速率(連續) | 2.2 slm (Ar) | |
RF功率(13.56 MHz) | 500 W | |
施加RF功率的持續時間 | 300秒 | |
循環(沉積+氮化)之數目 | 20個循環 |
關於比較例2,除了未進行氮化步驟外,經由PEALD在與實施例1相同之條件下於Si基板(Ф300 mm)上沉積氧化矽膜。
於將各基板自反應室取出後,使用DHF (100:1)持續1分鐘進行濕式蝕刻作為總共4個循環的一個循環。圖4顯示:以-♦-指示之圖(「僅沉積」)顯示氧化矽膜(比較例2)之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WERR [/TOX]」)、及應用於氧化矽膜之濕式蝕刻循環數目(「濕式蝕刻循環」)之間的關係,及以-▲-指示之圖(「經處理」)顯示併入氮之氧化矽膜(實施例1)之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WERR [/TOX]」)、及應用於氧化矽膜之濕式蝕刻循環數目(「濕式蝕刻循環」)之間的關係。如由圖4可見,併入氮之氧化矽膜展現實質上與熱氧化物膜相當之驚人改良的耐濕式蝕刻性,而未併入氮之氧化矽膜展現高濕式蝕刻速率,即不良的耐濕式蝕刻性。此外,圖4顯示氮不僅於表面上併入至氧化矽膜中,並且亦穿過表面且其到達特定深度,此乃因即使於四個循環的濕式蝕刻後,WERR仍然低。
此外,使實施例1中之併入氮的氧化矽膜經受其他分析。圖16係顯示併入氮之氧化矽膜隨時間經過(「經過時間[dd:hh:mm]」)之於633 nm下之折射率(「RI@633nm」)變化及應力(「應力 [MPa]」)變化的圖。如圖16所示,膜的RI及應力未改變,且實質上維持穩定達暴露至大氣空氣的2.5天,及甚至於暴露至大氣空氣7天後(未顯示)。藉由此技術獲得之併入氮之氧化矽膜係高度穩定的膜。
實施例
2
除了循環(沉積+氮化)數目為5替代實施例1中之20外,以與實施例1相同之方式利用PEALD將併入氮之氧化矽膜形成於具有深度110 nm、寬度30 nm、及間距60 nm之溝槽的Si基板(Ф300 mm)上。
於將各基板自反應室取出後,使用DHF(200:1)持續1分鐘來進行濕式蝕刻。圖5顯示橫截面圖的STEM照片,其顯示剛沉積於溝槽中之併入氮之氧化矽膜(「剛沉積」)及顯示重疊於照片上、封於方框中之於濕式蝕刻後之併入氮的氧化矽膜(「於濕式蝕刻後」)。如由圖5可見,當沉積併入氮之氧化矽膜時,其保形性高(約99%),及於濕式蝕刻後,驚人地,高保形性實質上經維持(約97%),即沉積於溝槽側壁上之部分的膜幾乎未被移除。與圖3相比,差異顯著。此意謂氮化不僅可在沉積於頂表面上之部分的膜,並且亦可在沉積於溝槽側壁上之部分的膜改良膜品質。
圖6顯示與圖5相似之STEM照片之放大部分圖,其顯示剛沉積之併入氮之氧化矽膜的層結構(「剛沉積」)。可確認存在五個以深灰色指示的氮氧化矽層。
實施例
3
利用PEALD以與實施例1類似之方式在下表2中顯示之條件下經由改變RF功率於Si基板(Ф300 mm)上形成併入氮之氧化矽膜。
表2 (數字為近似值)
參數 | ||
沉積循環(PEALD) | 基板溫度 | 300°C |
壓力 | 400 Pa | |
前驅物脈衝 | 0.5 秒 (BDEAS) | |
氧化氣體之流動速率(連續) | 0.8 slm (N2 O) | |
載送氣體之流動速率(連續) | 1.5 slm (He) | |
稀釋氣體之流動速率(連續) | 0.7 slm (He) | |
RF功率(13.56 MHz) | 變化,見圖10 | |
RF功率脈衝 | 1.5秒 | |
循環數目 | 30個循環 | |
氧化物膜的厚度 | 約33 nm | |
氮化處理 | 基板溫度 | 300°C |
壓力 | 400 Pa | |
氮源氣體之流動速率(連續) | 0.8 slm (N2 ) | |
載送氣體之總流動速率(連續) | 1.5 slm (He) | |
稀釋氣體之總流動速率(連續) | 0.7 slm (He) | |
RF功率(13.56 MHz) | 500 W | |
施加RF功率的持續時間 | 300秒 | |
循環(沉積+氮化)之數目 | 20個循環 |
將各基板自反應室取出後,使用具有633 nm波長之光測量R.I. (折射率)。圖10係顯示在併入氮之氧化矽膜之R.I.(「R.I. @633nm」)與用來沉積氧化矽膜之RF功率(「沉積RF功率」)之間之關係的圖。如由圖10可見,當使用200 W或以下之RF功率沉積併入氮之氧化矽膜時,所得併入氮之氧化矽膜之R.I.超過1.500,即較利用300 W或以上之RF功率形成之併入氮之氧化矽膜含有更多Si-N鍵,指示當用來沉積氧化矽膜之RF功率為200 W或以下時,氮可更平順地併入至氧化矽膜中。
實施例
4
及比較例
3
在實施例4中,利用PEALD以與實施例1相同之方式於Si基板(Ф300 mm)上形成併入氮之氧化矽膜。關於比較例3,除了未進行氮化步驟外,利用PEALD在與實施例4相同之條件下於Si基板(Ф300 mm)上沉積氧化矽膜。使所得之併入氮之氧化矽膜經受傅立葉變換紅外(FT-IR)光譜分析。圖11係根據實施例4之併入氮之氧化矽膜(「a:經處理」)及根據比較例3之氧化矽膜(「b:僅沉積」)的傅立葉變換紅外(FT-IR)光譜。如圖11中顯示,未經處理之膜(「b:僅沉積」)顯示於1065 cm-1
處之峰(Si-O伸縮振動)及於810 cm-1
處之峰(Si-O變形振動),指示此膜實際上為氧化矽膜。經過處理之膜(「a:經處理」)展現波數位移及較寬廣光譜,例如,1065 cm-1
處之峰(Si-O伸縮振動)位移至較低波數,指示形成新鍵諸如Si-N鍵(如此係SiN膜,則將會觀察到於880 cm-1
處之峰)(部分取代Si-O鍵),並重疊有歸屬於Si-O鍵之峰及歸屬於新鍵之峰。以上顯示氮藉由處理併入至膜中。
實施例
5
及比較例
4
在實施例5中,利用PEALD以與實施例4相同之方式於Si基板(Ф300 mm)上形成併入氮之氧化矽膜,且循環(沉積+氮化)數目為50替代實施例4中之20,此外,所得膜厚度為約80 nm替代實施例4中之約33 nm。關於比較例4,除了未進行氮化步驟外,利用PEALD在與實施例5相同之條件下於Si基板(Ф300 mm)上沉積氧化矽膜。使所得併入氮之氧化矽膜進行X-射線光電子光譜術(XPS)分析。圖13係根據實施例5之併入氮之氧化矽膜(「經處理」)於膜之深度方向中及根據比較例4之氧化矽膜(「僅沉積」)於膜之深度方向中之X-射線光電子光譜術(XPS) 的分析結果。如圖13所示,在併入氮之氧化矽膜(「經處理」)中,氮實質上均勻地成功併入至整個膜中並取代氧,即Si-N鍵經由取代反應部分取代Si-O鍵(膜包含10.6原子%之氮)。
實施例
6
及比較例
5
在實施例6中,利用PEALD以與實施例4相同之方式於Si基板(Ф300 mm)上形成併入氮之氧化矽膜,除了在氮化處理中使用He替代Ar作為稀釋氣體,以及所得膜厚度為約32 nm替代實施例4中之約33 nm。關於比較例4,除了未進行氮化步驟外,利用PEALD在與實施例6相同之條件下於Si基板(Ф300 mm)上沉積氧化矽膜。使所得之併入氮之氧化矽膜經受傅立葉變換紅外(FT-IR)光譜分析。圖12係根據實施例6之併入氮之氧化矽膜(「a:經處理」)及根據比較例5之氧化矽膜(「b:僅沉積」)的傅立葉變換紅外(FT-IR)光譜。如圖12中顯示,與圖11相似,未經處理之膜(「b:僅沉積」)顯示於1065 cm-1
處之峰(Si-O伸縮振動)及於810 cm-1
處之峰(Si-O變形振動),指示此膜實際上為氧化矽膜。經過處理之膜(「a:經處理」)展現波數位移及較寬廣光譜,例如,1065 cm-1
處之峰(Si-O伸縮振動)位移至較低波數且於810 cm-1
處之峰(Si-O變形振動)消失,指示氮藉由處理併入至膜中。
實施例
7
及比較例
6
在實施例7中,利用PEALD以與實施例6相同之方式於Si基板(Ф300 mm)上形成併入氮之氧化矽膜,除了沉積循環中之循環數目為600替代實施例6中之30及循環(沉積+氮化)數目為1替代實施例6中之20,以及所得膜厚度為約35 nm替代實施例6中之約33 nm。關於比較例6,除了未進行氮化步驟外,利用PEALD在與實施例7相同之條件下於Si基板(Ф300 mm)上沉積氧化矽膜。使所得之併入氮之氧化矽膜經受傅立葉變換紅外(FT-IR)光譜分析。圖14係根據實施例7之併入氮之氧化矽膜(「a:經處理」)及根據比較例6之氧化矽膜(「b:僅沉積」)的傅立葉變換紅外(FT-IR)光譜。如圖14中顯示,與圖11相似,儘管氮化處理僅於沉積循環後進行一次,但經過處理之膜(「a:經處理」)展現波數位移及較寬廣光譜,例如,1065 cm-1
處之峰(Si-O伸縮振動;在此光譜中,峰係於1062.2 cm-1
處測得)位移至較低波數(1060.0 cm-1
),指示氮藉由處理併入至膜中。
亦使膜進行其他分析以確定其性質。結果顯示於下表3。
如表3所示,即使當氮僅併入於頂部層中時(其經轉變為氮氧化矽層),膜性質亦顯著地改良,其中特定而言,濕式蝕刻速率(「WERR」)及漏電流顯著地改良。R.I.及FT-IR峰因併入氮而輕微地改變。
圖15係顯示根據實施例7之併入氮之氧化矽膜(「a:經處理」)及根據比較例6之氧化矽膜(「b:僅沉積」)之相對於熱氧化物膜之濕式蝕刻速率(「WERR [/TOX]」)及濕式蝕刻循環數目(「濕式蝕刻循環[次數]」)之間之關係圖。如圖15所示,經受第一濕式蝕刻循環之併入氮之氧化矽膜的最上層(「經處理」)展現低於1.0之顯著低的濕式蝕刻速率,指示氮穿透表面且有效地併入於最上層中。然而,在第二及第三濕式蝕刻循環,膜的濕式蝕刻速率展現與未經處理之膜(「僅沉積」)一般高的濕式蝕刻速率,此乃因僅穿透表面區域並併入於膜之最上層中的氮藉由第一濕式蝕刻循環移除。
根據文中揭示之技術,氮氧化矽層可於任何期望的位置形成,例如,僅於頂表面上,僅於界面區域(底部),以條紋圖案,或在整個膜中實質上地均勻。
熟悉本技藝者將理解,在不脫離本發明之精神的情況下,可進行大量及各種修改。因此,應清楚理解,本發明之形式僅為例示說明性的,而不意欲限制本發明之範疇。
1:基板
2:導電之平板電極;下台(下部電極)
3:反應室
4:導電之平板電極;上部電極;噴淋板
5:轉移室
6:排氣管線
7:排氣管線
11:內部(反應區)
12:電接地
13:圓管
14:分隔板
16:內部(轉移區)
20:HRF功率
21:氣體管線
22:氣體管線
23:氣體管線
24:密封氣體管線
a:閥
b:閥
c:閥
d:閥
e:閥
f:閥
S1:步驟
S2:步驟
S3:步驟
S4:步驟
S5:步驟
現在將參考意欲例示說明而非限制本發明之較佳具體例的圖式來描述本發明之此等及其他特徵。該等圖式經大大簡化以用於例示說明性目的且未必按比例繪製。
圖1A係用以沉積關於本發明之一具體例之介電膜之PEALD(電漿增強型原子層沉積)設備的示意圖。
圖1B繪示可用於本發明之一具體例中的使用流通系統(flow-pass system,FPS)之前驅物供應系統的示意圖。
圖2係顯示氧化矽膜之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WER Tox 比」)、及用於沉積氧化矽膜之RF功率(高頻)(「HRF」)之間的關係圖。
圖3顯示橫截面圖的STEM (掃描穿透式電子顯微鏡)照片,其顯示剛沉積於溝槽中之氧化矽膜(「剛沉積」)及顯示重疊於照片上、封於方框中之於濕式蝕刻後的氧化矽膜(「於濕式蝕刻後」)。
圖4根據本發明之一具體例顯示:以-♦-指示之圖(「僅沉積」)顯示氧化矽膜之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WERR [/TOX]」)、及應用於氧化矽膜之濕式蝕刻循環數目(「濕式蝕刻循環」)之間的關係,及以-▲-指示之圖(「經處理」)顯示併入氮之氧化矽膜之濕式蝕刻速率相對於熱氧化物膜之濕式蝕刻速率(「WERR [/TOX]」)、及應用於氧化矽膜之濕式蝕刻循環數目(「濕式蝕刻循環」)之間的關係。
圖5顯示根據本發明之一具體例之橫截面圖的STEM照片,其顯示剛沉積於溝槽中之併入氮之氧化矽膜(「剛沉積」)及顯示重疊於照片上、封於方框中之於濕式蝕刻後之併入氮的氧化矽膜(「於濕式蝕刻後」)。
圖6顯示與圖5相似之STEM照片之放大部分圖,其顯示剛沉積之併入氮之氧化矽膜的層結構(「剛沉積」)。
圖7繪示根據一具體例之併入氮之氧化矽膜之形成的示意性製程序列,其中各欄的寬度不一定代表實際的時間長度,且各列中線的高起水平代表開-狀態,而各列中線的底部水平代表關-狀態。
圖8顯示根據本發明之一具體例之氮化矽膜之沉積之示意性製程序列與氧化矽膜之氮化之示意性製程序列的組合,其中灰色格子表示「開」狀態(深灰色代表較高強度),而白色格子表示「關」狀態,且每一欄之寬度不表示各製程之持續時間。
圖9係說明根據本發明之一具體例形成具有期望層結構之併入氮之氧化矽膜之步驟的流程圖。
圖10係顯示根據本發明之一具體例在併入氮之氧化矽膜之RI(「R.I. @633nm」)與用來沉積氧化矽膜之RF功率(「沉積RF功率」)之間之關係的圖。
圖11係根據本發明之一具體例之併入氮之氧化矽膜(「a:經處理」)及根據一比較例之氧化矽膜(「b:僅沉積」)的傅立葉變換紅外(FT-IR)光譜。
圖12係根據本發明之另一具體例之併入氮之氧化矽膜(「a:經處理」)及根據另一比較例之氧化矽膜(「b:僅沉積」)的傅立葉變換紅外(FT-IR)光譜。
圖13係根據本發明之一具體例之併入氮之氧化矽膜(「經處理」)於膜之深度方向中及根據一比較例之氧化矽膜(「僅沉積」)於膜之深度方向中之X-射線光電子光譜術(XPS) 的分析結果。
圖14係根據本發明之一具體例之併入氮之氧化矽膜(「a:經處理」)及根據一比較例之氧化矽膜(「b:僅沉積」)的傅立葉變換紅外(FT-IR)光譜。
圖15係顯示根據本發明之一具體例之併入氮之氧化矽膜(「a:經處理」)及根據一比較例之氧化矽膜(「b:僅沉積」)之相對於熱氧化物膜之濕式蝕刻速率(「WERR [/TOX]」)及濕式蝕刻循環數目(「濕式蝕刻循環[次數]」)之間之關係圖。
圖16係顯示根據本發明之一具體例之併入氮之氧化矽膜隨時間經過(「經過時間[dd:hh:mm]」)之於633 nm下之折射率(「RI@633nm」)變化及應力(「應力 [MPa]」)變化的圖。
圖17示意性地繪示根據本發明之具體例由SiO層及SiON層構成的層狀結構,其中在(a)中SiON層構成最上層,在(b)中SiON層及SiO層於厚度方向中交替堆疊,及在(c)中SiON層構成底部層。
1:基板
2:導電之平板電極;下台(下部電極)
3:反應室
4:導電之平板電極;上部電極;噴淋板
5:轉移室
6:排氣管線
7:排氣管線
11:內部(反應區)
12:電接地
13:圓管
14:分隔板
16:內部(轉移區)
20:HRF功率
21:氣體管線
22:氣體管線
23:氣體管線
24:密封氣體管線
Claims (17)
- 一種併入氮之矽或金屬氧化物膜之形成方法,其包括以下步驟: (i)使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積矽或金屬氧化物膜,該電漿具有第一電漿密度;及 (ii)使用氮化氣體而不使用任何前驅物,經由電漿氮化該矽或金屬氧化物膜,該電漿具有較該第一電漿密度高之第二電漿密度。
- 如請求項1之方法,其進一步包括,在步驟(i)之前,(ii’)使用氮化氣體而不使用任何前驅物,經由電漿氮化該基板之表面。
- 如請求項1之方法,其中在步驟(i)中,該矽或金屬氧化物膜係經由電漿增強型原子層沉積(PEALD)來沉積。
- 如請求項3之方法,其中該氧化氣體包含氧及氮兩者。
- 如請求項3之方法,其中在步驟(i)中,該電漿係經由向電極施加RF功率所產生之電容耦合電漿,其中在PEALD之各循環中RF功率之持續時間係2.0秒或以下及RF功率之功率係每cm2 之基板表面0.28 W或以下。
- 如請求項5之方法,其中在步驟(ii)中,該電漿係經由向該等電極施加RF功率所產生,其中RF功率之功率係每cm2 之基板表面0.42 W或以上。
- 如請求項1之方法,其中步驟(i)及步驟(ii)係於相同反應空間或不同反應空間中進行,在步驟(i)及(ii)中向該(等)反應空間供應惰性氣體。
- 如請求項7之方法,其中在步驟(ii)中,該氮化氣體對該惰性氣體之流量比係1/99至50/50。
- 如請求項3之方法,其中步驟(ii)係於每1至100個循環之PEALD後重複地進行。
- 如請求項1之方法,其中該基板具有凹槽圖案且該矽或金屬氧化物膜係保形地沉積於該凹槽圖案上。
- 如請求項3之方法,其中在步驟(i)中,該電漿係經由向電極施加RF功率所產生之電容耦合電漿或於遠端電漿單元中產生之遠端電漿。
- 一種併入氮之矽或金屬氧化物膜之形成方法,其經由在期望位置將矽或金屬氧化物膜轉變為矽或金屬氮氧化物膜,此方法包括以下步驟: (a)設計併入氮之矽或金屬氧化物膜之層結構,該層結構係由以矽或金屬氧化物膜組成之層A及以矽或金屬氮氧化物膜組成之層B所構成; (b)根據該設計,關於該層A,使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積該矽或金屬氧化物膜,該電漿具有第一電漿密度;及 (c)根據該設計,關於該層B,使用氮化氣體而不使用任何前驅物,經由電漿以將該矽或金屬氧化物膜轉變為該矽或金屬氮氧化物膜之方式氮化該矽或金屬氧化物膜,該電漿具有較該第一電漿密度高之第二電漿密度。
- 如請求項12之方法,其中該併入氮之矽或金屬氧化物膜係由交替層疊之該層A的多個層及該層B的多個層所構成。
- 如請求項12之方法,其中該層A之總厚度對該層B之總厚度的比係0/100至99/1。
- 一種併入氧之矽或金屬氮化物膜之形成方法,其包括以下步驟: (i)使用含有矽或金屬之前驅物及氮化氣體,經由電漿於基板上沉積矽或金屬氮化物膜,該電漿具有第一電漿密度;及 (ii)使用氧化氣體而不使用任何前驅物,經由電漿氧化該矽或金屬氮化物膜,該電漿具有較該第一電漿密度低之第二電漿密度。
- 一種併入元素X之矽或金屬氧化物膜之形成方法,其包括以下步驟: (i)使用含有矽或金屬之前驅物及氧化氣體,經由電漿於基板上沉積矽或金屬氧化物膜,該電漿具有第一電漿密度;及 (ii)不使用任何用來沉積之前驅物,經由電漿激發含有元素X之氣體及將該元素X併入至該矽或金屬氧化物膜中,該電漿具有較該第一電漿密度高之第二電漿密度。
- 如請求項16之方法,其中該元素X係選自由B、C、Al、P、S、Ga、及As所組成之群。
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