TW202108806A - 使用雙(二乙基胺基)矽烷藉由peald沉積具有經改良品質之氧化矽膜的方法 - Google Patents

使用雙(二乙基胺基)矽烷藉由peald沉積具有經改良品質之氧化矽膜的方法 Download PDF

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TW202108806A
TW202108806A TW109128053A TW109128053A TW202108806A TW 202108806 A TW202108806 A TW 202108806A TW 109128053 A TW109128053 A TW 109128053A TW 109128053 A TW109128053 A TW 109128053A TW 202108806 A TW202108806 A TW 202108806A
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silicon oxide
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堅固山裕子
末盛秀美
中野竜
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荷蘭商Asm Ip私人控股有限公司
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Abstract

一種藉由電漿增強型原子層沉積(PEALD)於反應空間中於基材上使用雙(二乙基胺基)矽烷(BDEAS)沉積氧化矽膜之方法,PEALD的各重複沉積循環包含以下步驟:(i)在反應空間中在實質上抑制BDEAS之熱分解的氛圍中使BDEAS吸附在置於具有高於400 °C之溫度之基座上的基材上,及(ii)在反應空間中在氛圍中使其上吸附有BDEAS的基材暴露至氧電漿,藉此沉積一單層或次層的氧化矽。

Description

使用雙(二乙基胺基)矽烷藉由PEALD沉積具有經改良品質之氧化矽膜的方法
本發明大致係關於一種使用雙(二乙基胺基)矽烷(bis(diethylamino)silane, BDEAS)藉由電漿增強型原子層沉積(plasma-enhanced atomic layer deposition, PEALD)沉積具有經改良品質(例如,優異的耐化學劑性諸如低濕式蝕刻速率,尤其係於溝槽之側壁及底部處)之氧化矽膜的方法。
關於藉由PEALD沉積氧化矽膜之方法,已知一種使用BDEAS及氧電漿之沉積方法。然而,當使用習知方法在形成於基材中之溝槽中沉積氧化矽膜時,在溝槽之側壁及底部處的膜品質(耐化學劑性諸如低的乾或濕式蝕刻速率、漏電流、收縮率、平面內均勻度等)與在基材之頂表面上的膜品質相比傾向於不足或不令人滿意。一般而言,經由增加RF功率及/或RF功率脈衝之持續時間,預期膜品質可獲得改良。然而,當溝槽具有高縱橫比(例如,3或更高,尤其10或更高)時,歸因於電漿的方向性或各向異性特性(例如,由離子構成之直接電漿的離子轟擊),未達成膜品質的充分改良(尤其係於溝槽之側壁及底部處的膜品質)。
鑒於習知技術,本發明之一實施例提供一種使用BDEAS藉由PEALD沉積具有經改良品質之氧化矽膜的方法。
關於相關技術之問題及解決方案的任何討論,僅為提供本發明內文之目的而包括於本揭露中,且不應視為承認在本發明完成時已知該討論的任何或全部內容。
如以上所論述,在使用BDEAS藉由PEALD沉積氧化矽膜中,歸因於電漿的各向異性特性,作為製程參數,增加RF功率及/或RF功率脈衝之持續時間可能無法充分或有效地改良溝槽之側壁及底部處的膜品質。因此,作為製程參數,提高沉積溫度可被視為良好的選擇。然而,熟悉技藝人士可能認為BDEAS在高於400 °C之溫度下開始熱分解,及因此,為使用BDEAS獲得高品質的氧化矽膜,PEALD中之製程溫度較佳應為400 °C或更低。舉例來說,美國專利第8,227,032號陳述較佳在200與400 °C之間沉積具有極低碳及氫含量的高品質膜。如BDEAS熱分解,則產生胺、碳之氧化物、氮之氧化物、及矽之氧化物作為熱分解產物,從而導致沉積具有相當高之碳、氮、及氫含量的氧化矽膜。此外,例如,WO2016/954531陳述將晶圓表面加熱至約450 °C至約650 °C範圍內之溫度,使得經吸附的矽前驅物在晶圓表面上熱分解,從而形成一單層或次單層的矽膜。如以上所論述,熟悉技藝人士相當可能預期BDEAS亦在高於400 °C之溫度下熱分解。應注意,不同於其中含有碳/氮之經吸附矽前驅物與氧電漿反應及藉由用氧置換碳/氮之置換反應形成氧化矽膜的典型PEALD,於WO2016/954531中,首先,經吸附的矽前驅物於晶圓表面上熱分解形成一單層或次單層的矽膜,然後再暴露至氧源,藉此氧化矽膜從而形成SiO2 膜。
與熟悉技藝人士的預期相反地,本發明人發現BDEAS在高於400 °C但不高於650 °C之溫度下穩定且不會顯著地分解,及經由使用此一高溫作為藉由PEALD之沉積溫度,可顯著地改良所沉積之氧化矽膜的膜品質,尤其係於溝槽的側壁及底部處。在一些實施例中,在藉由PEALD於反應空間中於基材上使用BDEAS沉積氧化矽膜的方法中,PEALD的各重複沉積循環包含以下步驟:(i)在反應空間中在實質上抑制BDEAS之熱分解的氛圍中使BDEAS吸附在置於具有高於400 °C之溫度之基座上的基材上,及(ii)在反應空間中在氛圍中使其上吸附有BDEAS的基材暴露至氧電漿,藉此沉積一單層的氧化矽。
在一些實施例中,基座的溫度係低於650 °C。在一些實施例中,氛圍具有1,000 Pa或以下之壓力及5%至70%之氧濃度。此外,在一些實施例中,氛圍具有400 Pa或以下之壓力。又在一些實施例中,氛圍具有30%至60%之氧濃度。
為了概述本發明之態樣及所達成之優於相關技術之優點的目的,在本揭露中描述本發明之某些目標及優點。當然,應瞭解的是,可無須根據本發明之任何特定實施例來達成所有此類目標或優點。因此,例如,所屬技術領域中具有通常知識者將認知到,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教示或建議之其他目標或優點的方式來體現或實行本發明。
本發明之進一步的態樣、特徵及優點,將由下文的詳細描述而變得顯而易見。
在本揭露中,視上下文而定,「氣體(gas)」可包括汽化之固體及/或液體,並可由單一氣體或氣體混合物構成。同樣地,視上下文而定,冠詞「一(a/an)」係指一物種或包括多個物種之一屬系。在本揭露中,透過噴淋頭引入至反應室之製程氣體可包含胺基矽烷前驅物及添加劑氣體、基本上由胺基矽烷前驅物及添加劑氣體組成、或由胺基矽烷前驅物及添加劑氣體組成。前驅物可僅包含雙(二乙基胺基)矽烷(BDEAS)或包含作為第一前驅物之BDEAS及一或多種第二前驅物,該第二前驅物係不會干擾BDEAS之電漿氧化形成氧化矽之程度的胺基矽烷或非胺基矽烷。添加劑氣體可包括產生電漿之氣體,其用於在施加RF功率至添加劑氣體時激發前驅物以沉積氧化矽。添加劑氣體可包含用來氧化前驅物的反應物氣體且可進一步包含惰性氣體,該惰性氣體可在不會干擾電漿氧化形成氧化矽之程度上作為載體氣體及/或稀釋氣體饋送至反應室。前驅物及添加劑氣體可作為混合氣體或分開地引入至反應空間。前驅物可使用載體氣體(諸如,稀有氣體)引入。除了製程氣體以外之氣體(亦即,無通過噴淋頭的情況下引入之氣體)可用於例如密封反應空間,該氣體包括諸如稀有氣體之密封氣體。在一些具體例中,術語「前驅物」一般係指參與化學反應產生另一化合物之化合物,及特定言之係指一種構成膜基質或膜之主要骨架的化合物,而術語「反應物」係指除前驅物外之化合物,其活化前驅物、改質前驅物、或催化前驅物之反應,其中當施加RF功率時,該反應物可向膜基質提供元素(諸如O)並成為膜基質之一部分。術語「惰性氣體」係指當施加RF功率時激發前驅物之產生電漿之氣體,但不同於反應物,其未成為膜基質之一部分。
在一些實施例中,「單層」係指一分子厚的一層,及「次層」係指一子單位的層,其不一定係一單層而係在ALD之一個循環中作為最終膜之一子單位部分沉積的層。在一些實施例中,「膜(film)」係指實質上無針孔地在垂直於厚度方向之方向上連續地延伸以覆蓋整個目標或關注表面之層,或單純係覆蓋目標或關注表面之層。在一些實施例中,「層(layer)」係指形成於表面上之具有特定厚度之結構或者膜或非膜結構之同義詞。膜或層可由具有某些特性之離散單一膜或層或者由多個膜或層構成,且相鄰膜或層之間的邊界可明確或可不明確,並可基於物理、化學、及/或任何其他特性、形成製程或序列、及/或相鄰膜或層之功能或用途而建立。進一步地,在本揭露中,變數之任兩個數字可構成變數之可工作範圍,因為可工作範圍可基於例行工作判定,且所指示之任何範圍可包括或排除端點。此外,所指示的變數之任何數值(不管該等數值是否以「約」來指示)可指精確值或近似值並包括等效值,且在一些實施例中可指平均值、中值、代表值、多數值等。進一步地,在本揭露中,於一些實施例中,用語「由…構成(constituted by)」及「具有(having)」係獨立地指「一般或廣泛地包含(typically or broadly comprising)」、「包含(comprising)」、「基本上由…組成(consisting essentially of)」、或「由…組成(consisting of)」。在本發明中,於一些實施例中,任何已定義之意義未必排除尋常及慣例意義。
在本揭露中,於一些實施例中,「連續地(continuously)」係指不中斷真空、在時間線上無中斷、無任何材料插入步驟、未改變處理條件、其後立即、作為下一步驟、或在兩結構間無有別於該兩結構之插入的離散物理或化學結構。
在本揭露中,「步階(step)」或「凹部(recess)」係指任何結構,其具有形成在基材上之頂部表面、側壁、及底部表面,其可在高度方向上連續地串聯配置或者可係單一步階,且其可構成溝槽、通孔、或其他凹部。此外,在本揭露中,溝槽係任何包括孔洞/通孔的凹部圖案,且其在一些實施例中具有10至50 nm(通常15至30 nm)之寬度(其中當溝槽具有與寬度實質上相同的長度時,將其稱作孔洞/通孔,且其直徑為10至50 nm),30至200 nm(通常50至150 nm)之深度,及3至20(通常3至10)之縱橫比。
在本揭示案中,SiO膜不僅包括SiO膜,並且視製程配方而定,亦包括SiOC膜、SiON膜、SiOCN膜或其類似物,其中該等膜名稱為縮寫,除非另外描述,否則僅以非化學計量方式指示膜類型(僅藉由主要組成元素指示)。
圖2顯示在根據本發明之一具體例之一個循環中之PEALD的示意性製程序列,其中灰色格子表示「開」狀態,而白色格子表示「關」狀態,且各欄之寬度不代表各製程的持續時間。第一步驟(「饋送」(feed))包含將BDEAS於一脈衝中饋送至反應空間及使BDEAS於反應空間中於實質上抑制BDEAS之熱分解的氛圍中吸附於置於具有高於400 °C(較佳高於500 °C但不高於650 °C)之溫度之基座上的基材上。一般而言,溫度愈高,則可預期所產生之氧化矽膜之膜品質的改良愈大,尤其係在溝槽之側壁及底部處,只要可於氛圍中充分或實質地抑制BDEAS的熱分解即可。較佳地,氛圍具有1,000 Pa或以下(更佳400 Pa或以下,例如,333 Pa至400 Pa)之壓力及5%至70%之氧濃度(更佳30%至60%之氧濃度),以致即使當分解溫度高時,亦可抑制BDEAS的熱分解。在一些實施例中,利用以400 sccm 至5600 sccm (較佳2000 sccm 至4400 sccm )之流動速率饋送的一或多種惰性氣體(例如,稀有氣體諸如Ar及/或He)將作為氧化劑的氧以400 sccm 至5600 sccm (較佳1600 sccm 至4000 sccm)之流動速率饋送至反應空間。關於氧化劑,亦可使用二氧化氮。在此實施例中,氧化劑係於整個沉積循環中連續地饋送。在「饋送」步驟中,BDEAS係使用載體氣體之流動饋送,該載體氣體係以2000 sccm之流動速率饋送的惰性氣體諸如稀有氣體(例如,Ar及/或He)。由於ALD係自限制吸附反應製程,因此所沉積的前驅物分子之量係由反應性表面位點之數目確定,且與飽和後的前驅物暴露無關,且前驅物之供應係使得反應性表面位點在每個循環飽和(「化學吸附」係指化學飽和吸附)。在此實施例中,載體氣體係於整個沉積循環中連續地饋送。
載體氣體之連續流動可使用流通系統(FPS)來完成,其中載體氣體管線設有具有前驅物儲槽(瓶)的歧路管線,且主要管線與歧路管線經切換,其中當僅欲將載體氣體饋送至反應室時,歧路管線經關閉,而當欲將載體氣體及前驅物氣體兩者均饋送至反應室時,關閉主要管線且載體氣體流過歧路管線並從瓶與前驅物氣體一起流出。以此方式,載體氣體可連續地流入反應室中,且可藉由於主要管線與歧路管線之間切換而以脈衝載送前驅物氣體。圖1B繪示根據本發明之一實施例之使用流通系統(FPS)的前驅物供應系統(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)之載體氣體流過具有閥b及c之氣體管線,接著進入瓶(儲槽)20。載體氣體自瓶20流出,同時載運對應於瓶20內之蒸氣壓力的量之前驅物氣體,並流過具有閥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經關閉。當僅將載體氣體(稀有氣體)饋送至反應室時,如圖1B中之(b)所示,載體氣體流過具有閥a之氣體管線,同時繞過瓶20。在上文中,閥b、c、d、e、及f經關閉。
在一些實施例中,「饋送」的持續時間係0.1秒至3.0秒(較佳0.2秒至0.5秒)。
接下來,在第二步驟(「沖洗-1」)中,沖洗反應空間以將過量的BDEAS及未吸附的BDEAS自基材表面移除。沖洗可簡單地經由使氧化劑及作為沖洗氣體之載體氣體連續流動來完成,儘管亦可使用另外的沖洗氣體。在一些實施例中,沖洗的持續時間係0.2秒至2.0秒(較佳0.3秒至1.0秒)。在一些實施例中,在PEALD中,經由縮短沖洗的持續時間(例如,至0.1秒至0.5秒之範圍),一些未吸附的BDEAS可能殘留於頂表面上及溝槽中,且此會導致降低頂表面上及溝槽底部處的膜品質,同時使側壁上之膜品質改良至特定程度。此可能係由於較短的沖洗持續時間於溝槽中留下更多的BDEAS,其會如同雲般地停留於溝槽中而部分阻擋電漿到達底部,同時則有更多電漿能量到達側壁。
接下來,在第三步驟(「RF脈衝」)中,使吸附於基材表面上之BDEAS暴露至氧電漿,藉此於基材上沉積一單層或次層的氧化矽。在一些實施例中,RF功率施加的期間(暴露至電漿之期間)係在0.2秒至2.0秒之範圍內(較佳0.2秒至1.2秒)。當使用導電耦合的平行電極時,也可藉由改變上及下部電極間的距離來調整電漿暴露時間,其中藉由增加距離,在前驅物進入反應空間的流動速率不變時,可延長前驅物滯留在上與下部電極之間之反應空間中的滯留時間。在一些實施例中,上及下部電極間的距離(mm)係7.5 mm至13 mm(較佳7.5 mm至10 mm)。在一些實施例中,如針對300-mm晶圓所量測(其可針對不同尺寸晶圓轉換為W/cm2 之單位),用來沉積的RF功率(W)(例如,13.56 MHz)係50 W至1000 W(較佳200 W至500 W)。
於第三步驟後,在第四步驟(「沖洗-2」)中,沖洗反應空間以自基材表面移除未反應的BDEAS及反應副產物。沖洗可簡單地經由使氧化劑及作為沖洗氣體之載體氣體連續流動來完成,儘管亦可使用另外的沖洗氣體。在一些實施例中,沖洗的持續時間係0.1秒至1.0秒(較佳0.1秒至0.3秒)。
例如,可使用包括圖1A所繪示之設備的任何合適設備來執行製程循環。圖1A係可用於本發明之一些實施例中之PEALD設備(所欲的係與經程式化以實施下述序列之控制機構協力)的示意圖。在此圖式中,藉由在反應室3的內部11(反應區)中提供彼此平行且面對的一對導電平板電極4、2,施加HRF功率(13.56 MHz或27 MHz)25至一側並將另一側12電氣接地而在電極之間激發電漿。溫度調節器係在下部台2(下部電極)中提供,且放置在其上之基材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,且反應物氣體及/或稀釋氣體(若有的話)以及前驅物氣體係分別通過氣體管線21及氣體管線22以及通過噴淋板4引入至反應室3中。此外,在反應室3中,提供具有排氣管線7之圓管13,通過其排出反應室3之內部11中的氣體。此外,設置在反應室3下方之傳送室5具備密封氣體管線24,以經由傳送室5的內部16(傳送區)將密封氣體引入至反應室3的內部11中,其中提供用於分開反應區與傳送區之分隔板14(此圖式省略閘閥,晶圓係通過該閘閥傳送至傳送室5中或從該傳送室傳送)。傳送室亦具備排氣管線6。在一些實施例中,多元素膜沉積及表面處理係在相同反應空間中執行,使得所有步驟可連續地實施,而不使基材暴露至空氣或其他含氧大氣。
在一些實施例中,於圖1A所描繪之設備中,可在實質上不使反應室壓力波動的情況下使用圖1B所繪示之切換惰性氣體流及前驅物氣體流的系統(先前描述)以脈衝引入前驅物氣體。
所屬技術領域中具有通常知識者應瞭解,設備包括一或多個控制器(未圖示),其(等)經程式化或以其他方式組態以導致實施本文於別處所述之沉積及反應器清潔製程。如所屬技術領域中具有通常知識者將瞭解的,(多個)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訊。
在一些實施例中,可使用雙室反應器(經設置為彼此靠近之用於處理晶圓的兩個區段或隔室),其中反應物氣體及稀有氣體可通過共用管線供應,而前驅物氣體係通過非共用管線供應。
具有填充能力的膜可應用至各種半導體裝置,包括但不限於,3D交叉點記憶體裝置中的晶胞絕緣、自對準貫孔、偽閘(替換當前的多晶矽)、反相圖案化、PC RAM絕緣、切割硬遮罩、及DRAM儲存節點接觸(SNC)絕緣。
實例
在未指定條件及/或結構之下列實例中,所屬技術領域中具有通常知識者可鑒於本揭露而按照例行實驗輕易地提供此類條件及/或結構。所屬技術領域中具有通常知識者將理解,實例中所用的設備包括一或多個控制器(未圖示),其經程式化或以其他方式經組態以致使如本文於別處所述之沉積及反應器清潔製程之實施。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訊。
參考實例 1(BDEAS 之熱穩定性 )
在參考實例1中,為檢驗BDEAS的熱穩定性,將其上形成具有1.20 nm厚度之原生或天然氧化物膜的Si基材置於具有圖1B中所繪示之氣體供應系統(FPS)之圖1A中所繪示的設備中。經由在未向反應室施加RF功率之情況下在400 Pa之壓力下向其中饋送2000 sccm之BDEAS及2000 sccm之氧來控制反應室之氛圍,其中將基座溫度設定於400 °C至650 °C之範圍。於基座溫度達到設定溫度後800秒,於各設定溫度下測量膜厚度。作為比較參考實例,以與參考實例1相同之方式於各設定溫度下測量膜厚度,僅除了未向反應室饋送BDEAS。
圖3顯示指示於膜厚度與基座溫度間之示意關係的圖。如圖3所示,具有BDEAS饋送之膜厚度(「有饋送」)及沒有BDEAS饋送之膜厚度(「無饋送」)在整個溫度範圍中實質上相同。應注意看來隨溫度增加的膜厚度即使當未饋送BDEAS時亦變得較高,此係由於基材本身(具有下伏的天然氧化物膜)進一步經氧氧化,從而提高視厚度。此外,在550 °C、600 °C、及650 °C之溫度下當饋送BDEAS時的膜厚度稍大於未饋送BDEAS之情況。此係由於BDEAS藉由熱吸附於基材表面上。如BDEAS在設定溫度下已熱分解,則經分解的組分(諸如胺、碳之氧化物、氮之氧化物、及矽之氧化物)將連續累積於基材表面上,從而顯著提高膜厚度,尤其係在較高溫度下。因此,圖3中顯示的結果證實BDEAS在400 °C至650 °C之溫度範圍內未熱分解。
實例 1( 在高沉積溫度下的膜品質改良 )
使用圖1A所繪示之設備及圖1B所繪示之氣體供應系統(FPS),在圖2所繪示之製程序列中在下文表1所示的條件下(改變沉積溫度),藉由PEALD製程將氧化矽膜沉積在Si基材(具有300 mm直徑及0.7 mm厚度)上,Si基材具有溝槽,溝槽具有大約30 nm的開口,並具有大約90 nm的深度(縱橫比大約3),以確定膜的膜品質。於完成氧化矽膜的沉積後,使用STEM拍攝具有溝槽之每一基材的橫截面圖。
表1(數字係近似值)
溫度設定 基座溫度(°C)。 見圖4
沉積 壓力(Pa) 400
電極間隙(mm) 7.5
饋送時間(秒) 0.2
沖洗-1(秒) 0.3
RF時間(秒) 1
沖洗-2(秒) 0.1
RF功率(W) 500
前驅物 BDEAS
載體 Ar
載體流量(slm) 2.0
稀釋Ar (slm) 2.0
密封He (slm) 0.2
O2 (slm) 4.0
循環數目 500
於完成各氧化矽膜(於頂表面上具有25 nm之平均膜厚度)的沉積後,使基材經受濕式蝕刻(經由將基材於具有1%濃度之dHF溶液中在22 °C下浸漬30秒)。此外,於濕式蝕刻後,使用STEM拍攝具有溝槽之每一個基材的橫截面圖。
圖4係顯示經受在不同溫度下之氧化矽膜沉積(「剛沉積」),隨後接著濕式蝕刻(「於DHF浸漬後」)之溝槽之橫截面圖之STEM照片的圖。在圖4中,「側面/頂部[%]」係指當沉積至頂部部分時之側壁部分之厚度的比率[%],及「WERR [TOX比]」係指各部分的濕式蝕刻速率相對於標準熱氧化物膜的濕式蝕刻速率。如圖4所示,當沉積溫度為400 °C或更高,尤其高於500 °C(更佳550 °C或更高)時,側壁部分的膜品質獲得改良。
實例 2( 利用其他參數之膜品質的改良 )
除了示於下表2之條件外,以如實例1之相同方式將氧化矽膜沉積於Si基材上。
表2(數字係近似值)
  UHT-6 UHT-7 UHT-8 UHT-9 UHT-10 UHT-11
溫度設定 基座溫度(°C) 650
沉積 壓力(Pa) 400 400 1000 3000 400 400
沖洗-1(秒) 0.3 2 2 2 0.3 0.3
載體Ar (slm) 2.0 2.0 2.0 2.0 2.0 0.4
稀釋Ar (slm) 2.0 2.0 2.0 2.0 5.6 2.0
O2 (slm) 4.0 4.0 4.0 4.0 0.4 5.6
O2/(O2+Ar) (%) 50 50 50 50 5 70
於完成各氧化矽膜的沉積後,以與實例1相同之方式使基材經受濕式蝕刻。此外,於濕式蝕刻後,使用STEM拍攝具有溝槽之每一個基材的橫截面圖。應注意當於UHT-9中沉積壓力為3,000 Pa 時,膜沉積變得高度異常,及因此,未進行此樣本的濕式蝕刻評估。
圖5係顯示經受在不同壓力、不同氧濃度、及不同沖洗持續時間下之氧化矽膜沉積(「剛沉積」),隨後接著濕式蝕刻(「於DHF浸漬後」)之溝槽之橫截面圖之STEM照片的圖。在圖5中,「側面/頂部[%]」及「WERR [TOX比]」指示如同圖4中之相同意義。如圖5所示,在高沉積溫度(650 °C)下,當於UHT-7中沉積壓力為400 Pa時,相較於在UHT-8中(1,000 Pa),側壁部分的膜品質獲得改良。然而,相較於在UHT-8中(1,000 Pa),在UHT-7中400 Pa之壓力下頂部部分的膜品質未獲得改良,且相較於在UHT-8中(1,000 Pa),在UHT-7中400 Pa之壓力下底部部分的膜品質變差。此可能係由於由各部分之表面所接受到之電漿轟擊將係呈頂部(400 Pa) > 頂部 (1000 Pa) > 底部 (400 Pa) > 底部 (1000 Pa) > 側面 (400 Pa) > 側面 (1000 Pa)之次序,且在底部 (1000 Pa)附近將存在用來改良膜品質的最佳電漿轟擊,及當電漿轟擊高於或低於最佳電漿轟擊時,如圖7中示意性地繪示,膜品質將獲得較低程度的改良。電漿係具高自由電子含量(約50%)的部分游離氣體,且當電漿係藉由在平行電極之間施加AC電壓來激發時,離子藉由在電漿鞘與下部電極之間發展出的自dc偏壓 (VDC )加速並在垂直於膜的方向(離子入射方向)上轟擊置於下部電極上之基材上的膜。基於此非限制性理論,熟悉技藝人士將能夠經由操控沉積壓力而視需要地調整各部分的膜品質(如此,可在實質上相同的程度下調整底部部分的膜品質及側壁部分的膜品質(及另外頂部部分的膜品質)。電漿的轟擊可由電漿密度(電漿活性物種之量)或離子的動能來表示,及電漿密度可如美國專利公開案第2017/0250068號中所揭示來評估,將其全體揭示內容以引用的方式併入本文。
此外,如圖5中顯示,在高沉積溫度(650 °C)下,當於UHT-6中氧化劑氣體(於此實施例中為氧加上氬)中之氧濃度為50%時,相較於在 UHT-10 (5%)及 UHT-11 (70%)中,側壁部分的膜品質獲得改良。然而,相較於在UHT-10 (5%)及UHT-11 (70%)中,UHT-6中於50%之氧濃度下頂部部分的膜品質變差。此可能係由於不僅氧電漿、並且氬電漿亦有助於側壁部分的膜品質,及當氧濃度及氬濃度之比率大致相等(例如,±10%,即,40%至60%)時,側壁部分的膜品質可顯著地改良。基於此非限制性理論,熟悉技藝人士將能夠經由操控氧濃度而視需要地調整各部分的膜品質。
此外,如圖5所示,在高沉積溫度(650 °C)下,當於UHT-6中沖洗持續時間為0.3秒時,相較於在UHT-7 (2.0秒)中,側壁部分的膜品質獲得改良。然而,相較於在UHT-7 (2.0秒)中,在UHT-6中在0.3秒之沖洗持續時間下頂部部分的膜品質及底部部分的膜品質變差。此可能係由於在0.3秒之沖洗持續時間中一些未吸附的BDEAS可能殘留於頂表面上及溝槽中,且此會導致頂部部分的膜品質及底部部分的膜品質降低,同時使側壁部分的膜品質改良至特定程度。此可能係由於較短的沖洗持續時間於溝槽中留下更多的BDEAS,其會如同雲般地停留於溝槽中而部分阻擋電漿到達底部,同時則有更多電漿能量到達側壁。基於此非限制性理論,熟悉技藝人士將能夠經由操控氧濃度而視需要地調整各部分的膜品質。
實例 3( 膜品質的改良 - 覆式沉積 )
以與實例1相同的方式(僅除了此係毯覆式沉積(非圖案沉積)外)將氧化矽膜沉積於沒有溝槽的Si基材上。
於完成各氧化矽膜的沉積後,以與實例1相同的方式使基材經受濕式蝕刻。此外,於濕式蝕刻後,就平均厚度、平面內厚度均勻度、及濕式蝕刻速率來評估各氧化矽膜的膜性質。
圖6係顯示使用於圖4顯示之沉積中之沉積條件、及所產生之氧化矽膜之膜性質的圖,包括藉由膜之2D彩色映射分析之薄膜厚度輪廓測量之影像的彩色版本。在圖6中,「第一WERR/TOX」係指針對濕式蝕刻之第一分鐘所量測之各膜之濕式蝕刻速率相對於標準熱氧化物膜的濕式蝕刻速率,同時「第二WERR/TOX」係指針對濕式蝕刻之第二分鐘所量測之各膜之濕式蝕刻速率相對於標準熱氧化物膜的濕式蝕刻速率。如圖6所示,在高沉積溫度(650 °C)下,當於UHT-9中沉積壓力為3,000 Pa時,相較於在UHT-6、-7、及-8 (400 Pa)中,膜沉積高度異常,且未評估膜品質。此外,當於UHT-8中沉積壓力為1,000 Pa時,相較於在UHT-6及-7 (400 Pa)中,膜品質變差,儘管其係在正常沉積內。此外,如圖6所示,5%至70%之氧濃度為用來提供適當膜品質的可工作範圍。
所屬技術領域中具有通常知識者將了解,在不偏離本發明之精神的情況下,可作出大量及各種修改。因此,應清楚瞭解,本發明之形式僅係說明性,而非意欲限制本發明之範疇。
1:基材 2:導電平板電極 3:反應室 4:導電平板電極 5:傳送室 6:排氣管線 7:排氣管線 11:反應腔室之內部(反應區) 12:電接地之一側 13:圓管 14:分隔板 16:傳送室的內部(傳送區) 20:瓶(儲槽) 21:氣體管線 22:氣體管線 24:密封氣體管線 25:HRF功率 a:閥 b:閥 c:閥 d:閥 e:閥 f:閥
現將參照意欲說明而非限制本發明之較佳實施例的圖式來描述本發明的這些及其他特徵。圖式係經大幅度簡化以供說明性目的使用,且未必按比例繪製。
本專利或申請案檔案包含至少一個以彩色製作的圖式。具有彩色圖式之本專利或專利公開申請案的複本,將由專利局依申請並支付必要費用而提供。
圖1A係可用於本發明之一具體例中之用於沉積氧化矽膜之PEALD(電漿增強型原子層沉積)設備的示意圖式。
圖1B繪示可用於本發明之一具體例中之使用流通系統(flow-pass system, FPS)之前驅物供應系統的示意圖式。
圖2顯示在根據本發明之一具體例之一個循環中之PEALD的示意性製程序列,其中灰色格子表示「開」狀態,而白色格子表示「關」狀態,且各欄之寬度不代表各製程的持續時間。
圖3顯示指示參考實例1中於膜厚度與基座溫度間之示意關係的圖。
圖4係顯示經受在不同溫度下之氧化矽膜沉積(「剛沉積」),隨後接著濕式蝕刻(「於DHF浸漬後」)之溝槽之橫截面圖之STEM照片的圖。
圖5係顯示經受在不同壓力、不同氧濃度、及不同沖洗持續時間下之氧化矽膜沉積(「剛沉積」),隨後接著濕式蝕刻(「於DHF浸漬後」)之溝槽之橫截面圖之STEM照片的圖。
圖6係顯示使用於圖4顯示之沉積中之沉積條件、及所產生之氧化矽膜之膜性質的圖,包括藉由膜之2D彩色映射分析之薄膜厚度輪廓測量之影像的彩色版本。
圖7係顯示根據本發明之一實施例於一表面上之濕式蝕刻速率與電漿轟擊間之關係的示意圖。
1:基材
2:導電平板電極
3:反應室
4:導電平板電極
5:傳送室
6:排氣管線
7:排氣管線
11:反應腔室之內部(反應區)
12:電接地之一側
13:圓管
14:分隔板
16:傳送室的內部(傳送區)
21:氣體管線
22:氣體管線
24:密封氣體管線
25:HRF功率

Claims (9)

  1. 一種藉由電漿增強型原子層沉積(plasma-enhanced atomic layer deposition, PEALD)於反應空間中於基材上使用雙(二乙基胺基)矽烷(bis(diethylamino)silane, BDEAS)沉積氧化矽膜之方法,PEALD的各重複沉積循環包含以下步驟: (i)在該反應空間中在實質上抑制BDEAS之熱分解的一氛圍中使BDEAS吸附在置於具有高於400 °C之溫度之一基座上的該基材上,及 (ii)在該反應空間中在該氛圍中使其上吸附有BDEAS的該基材暴露至氧電漿,藉此沉積一單層或次層的氧化矽。
  2. 如請求項1之方法,其中該基座的溫度不高於650 °C。
  3. 如請求項1之方法,其中該氛圍具有1,000 Pa或以下之壓力及5%至70%之氧濃度。
  4. 如請求項3之方法,其中該氛圍具有400 Pa或以下之壓力。
  5. 如請求項3之方法,其中該氛圍具有30%至60%之氧濃度。
  6. 如請求項1之方法,其中各重複沉積循環進一步包括於步驟(i)與步驟(ii)之間沖洗該反應空間。
  7. 如請求項6之方法,其中該沖洗經進行低於2.0秒。
  8. 如請求項1之方法,其中該基材具有在步驟(i)中BDEAS吸附於其上的一圖案化步階。
  9. 如請求項8之方法,其中該圖案化步階係具有3或更高之縱橫比的一溝槽。
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