TW201220394A - Low-temperature dielectric film formation by chemical vapor deposition - Google Patents

Low-temperature dielectric film formation by chemical vapor deposition Download PDF

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TW201220394A
TW201220394A TW100134827A TW100134827A TW201220394A TW 201220394 A TW201220394 A TW 201220394A TW 100134827 A TW100134827 A TW 100134827A TW 100134827 A TW100134827 A TW 100134827A TW 201220394 A TW201220394 A TW 201220394A
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gas
process chamber
film
forming
substrate
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Anthony Dip
Kimberly G Reid
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Tokyo Electron Ltd
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Description

201220394 ， 六、發明說明： 【發明所屬之技術領域】 本發明係關於半導體基板處理，尤有關於使用氣化之石夕产斑 水蒸氣之低溫介電膜沉積之方法。 【先前技術"】 在半導體基板表面上之積體電路之形成過程中，氧化物戋氮 氧化物膜頻繁地生長或沉積在晶體基板(例如：矽)之表面上兴 例來說’用在半導體快閃記憶體與微特徵側壁應用(micr〇_featwe+ sidewall applications)之高品質氧化矽(si〇x，xg2)膜之化學氣相沉 積(CVD)之工業標準製程係以二氯矽烷(dCS)與一氧化二 之高溫反應為基礎。此製程之主要優點包含在批次製程中同^處 理多個基板之能力；氧化矽膜之良好電氣性能；以及相較於其他 CVD膜，膜之濕蝕刻速率相對低，該^^膜例如：使用矽^四 乙酯(TE0S，tetraethyl orthosilicate)、雙(叔丁胺基)矽烷(βΤΒΑ8， bis (tertiary-butylamino) silane)、與其他前導物所沉積之膜。 然而，有一些關於使用1)(：8與^0來執行氧化石夕膜之CVD 之缺點。當使氧化矽膜與需要低的熱預算之先進材料結合時，此 cvp製程需要可能會限制其使用之相當高之基板溫度(例如：約 800C)。並且’已發現使用n2〇氣體作為氧化氣體會導致不良與 普遍不可控制之氮(N)結合到氧化矽膜中。低的膜沉積率被認為是 由於氧化膜上之速率限制DCS成核步驟所造成，其因DCS與n2〇 間缺乏氣相反應所引起。 、 高K介電質之需求使製造業者必須藉由將氮結合至氧化物膜 中來加強現存之氧化物膜(例如：矽與鍺上之氧化物膜）。在此技藝 工眾所皆知，氮結合至氧化物膜會增加所產生氮氧化物膜之介電 取數，並且允許薄閘極介電質生長在這些半導體基板材料上。氮 氧化矽(si〇xNy)膜可以有良好的電氣特性，包含半導體應用中之裝 • 置運作所期望之尚電子遷移率(electron mobility)與低電子陷啡密 201220394 f (electron trap density)。氮結合至薄氧化石夕膜之 = 雜多晶㈣極、改善之介面平坦度、氮氧化石夕膜之 之增加、以及改善之障壁特性以避免金屬氧化物或金屬 閘極材料擴散至下方基板。 胃 由於半導體裝置之微型倾絲㈣之細（需少之半導 麟理方法之熱預算），有新處理方法之需求，賴處理方法提供 =制之深度具高氮結合之低溫氧化賴氮氧化頻沉積作用， 同時提供氧化物生長之控制速率。 【發明内容】 本發明之一實施例提供藉由使用二氯矽烷(Dcs)與水蒗 批次式處理系統中之數個基板上低溫cv〇氧化矽膜之方法、、。、詨方 :將數健板安置在製雜室巾；職健室加熱至彻 與少於650 C間之沉積溫度；將包含水蒸氣之第一製 ::ϊ;腔;:;將包含二氣鄭)之第二製程氣 月工至中，在製程腔室中建立少於2 T〇rr之氣體廢力；以及使第一 與第二製程氣體反應，以在數個基板上熱沉積氧化矽膜。另一每 施例更包含：在流動第-製程氣體與第二縣氣體時將 化氮_)氣體之第.三製減驗_製健室巾；以及使 膜與第三製程氣體反應，以在基板上形成氮氧化矽膜。 【實施方式】 本發明之實施例提供用來形成半導體裝置之介電膜之 積製程。在一實施例中，提供使用二氯石夕盥水蒸之 ，之非躲CVD方法。在另-實_巾，提供使^cs、水基 軋、與一氧化氮(NO，nitric oxide)氣體之氮氧化矽膜之非電漿cv〇 方法。本發明之實施例達到具有良好材料與電氣特性之二^化 與氮氧化矽膜之高沉積速率，同時使用比工業標準高溫 (HTO)製程(依賴基板上之DCS與-氧化二氮_，nitr()us。 之反應)更低之沉積溫度。 201220394 ί ’以水蒸氣氧化劑與非必要之1^。氣體取代N2〇 .i t Λ 频，允魏積溫度降低大於财c、大於 料夕或备甚300 c(例如：高達35〇。〇，同時提供有良好材 :、、’氧,賴’該良好材料特性包含相較於基線ΗΤ0製程之 Ιί=ϊί =積溫度之降低提供先進積體電路所需之熱預 ίίϊί降ΐ為受限制之熱預算不會允許基板_之增加， 益。更長之處辦間在轉體裝置之高量製造巾會稽合成本效 一水蒸氣氧化劑之使耻在_航積溫度下制 ，，速率’同時提供相當之氧化稍氮氧化賴之電I更 i^mN20之ητ〇製程，本發明之實施例提供用來精择控 ^氧化賴之Ν結合之機構。而且，可以選擇性地在高於沉 ，度=度下執行後沉積(p0st_deposition)熱處理，以進一步改盖氧 化矽與氮氧化矽膜之材料與電氣特性。 q #ifί希望受理論拘束’本發明者相信，不像被認為專門發 與Ν20間之反應，Dcs與水蒸氣間之氣 t面互相作用之前)能使基板表面上發生因dsc 裂解或聚=物之形成所產生之0(：8物種之改善核化作用。 1〇’顯示具有製程腔室12之批次式處理系統 而數個基板20女置在製程腔室12内。熟悉本技蔹 ί理士;= 示，述批次式處理系統1〇 ’本發明亦可^用於-次 ?理-個基板之早-式基板處理。圖2八與迚描述在圖【中之某 板20上個別形成氧化石夕與氮氧化石夕膜之製程流程圖。 " 驟參1與圖2兩者’在方法2〇0之一實施例中，在步 基板20㈣在製程腔室12中。基板20可以安 安置i 丨ίίϊΐ 13上。熟悉本技藝者將觀察到，將基板20 ίΜ""包含在基板20插入後透 過排乳口 15使製程腔室12排氣、以及透過真空口 μ 二將基板20安置於批次式處理系統10内也ΐ以‘ 3使職性乳體(例如：氮)來洗滌製程腔室12，以稀釋或減少製 201220394 程腔室12内之有機污染物之濃度。 在步驟204中，將製程腔室12加熱到4〇(rc與少於65〇〇C2 間之沉積溫度。在製程腔室12之加熱_，加熱速率可以從每分 鐘數度C到每分鐘1〇〇度c以上。 •在加熱之後，在步驟206中，將包含水蒸氣之第一製程氣體 ，過進氣口 16而導引到製程腔室12中。第一製程氣體包含水蒸 ，但不是氮化氣體。在步驟208中，將包含DCS與非必要之稀釋 氣體之第二製程氣體透過進氣口 17而導引到製程腔室12中。在 步驟210中，在製程腔室中建立低於21〇11>之製程氣體壓力。在 步驟212中，來自水蒸氣之氧與DCS於氣相中反應，並在各基板 20上沉積氧化矽膜。 現在參考圖1與圖3兩者，在方法3〇〇之另一實施例中，在 =驟302中，將數個基板2〇安置在製程腔室12中。基板2〇可以 安^在可旋轉基板支撐H 13上。熟悉本技藝者將觀察到，將基板 加安置或裝載到批次式處理系統1〇内可以包含在基板2〇插入之 後透過排氣口 15來使製程腔室12排氣、以及透過真空口 14來排 二製私腔室12。此外，將基板2〇安置於批次式處理系統1〇内也 了以包含使用惰性氣體(例如：氮)來洗條製程腔室12，以稀釋或 減少製程腔室12内之有機污染物之濃度。 〆 。在步驟304中，接著將製程腔室12加熱到4〇〇。〇與少於65〇 P之間之處理溫度。在製程腔室12之加熱期間，加熱/速率可以從 母分鐘數度C到每分鐘1〇〇度c以上。 、、在加熱之後，在步驟306中，將包含水蒸氣之第一製程氣體 透過進氣口 16而導引到製程腔室12中。在步驟3〇8中，將包含 DCS與非必要之稀釋氣體之第二製程氣體透過進氣口 口而導引到 製程腔室12中。在步驟310中，將包含N〇與非必要之稀釋氣體 之第三製程氣體導引到製程腔室中。在步驟312中，在製程腔室 中建立低於2 Torr之製程氣體壓力。在步驟314中，來自水^氣 之氧在氣相中與DCS和NO反應，如此來自NO之氮會結合至氧 化矽臈中，藉此在各基板20上形成氮氧化矽膜。 口 201220394 翕舻:己：：以^生處理環境之第-、第二、與非必要之第三f1程 處轉境有-處理壓力。本發明者了解處理玆ΐ 氣特性之0Li石良Γ均句度與料體裝置之所需材料與電 ::與 =:=r sr r-之間、1 τ:與 C之間、4,與45。。。之間、彻。。與5⑻。c之間、解。、與55〇 間、500C與 60(TC之間、55(rc^ 6G(rc之間、55(rc盘少於 im、或_°c與少於65〇t之間之沉積溫度。在一 Ϊ施例 己:ί理溫度來設定處理愿力’以控制氧化石夕或氮氧化石夕膜 =積速率。熟悉本技藝者將觀察到，在航積_，處理屢力、 會fi。因此，「設定」一詞並不限制於設定處理 屋力、乳體流速、或處理溫度之單—動作。更確切地說，設定可 以代表任何數目之設定或調整動作，如此係依據來自内部控制、 來自產業、或者由客戶所決定之任何品質鮮來沉積氧化梦 氮氧化賴。第-、第二、以及非必要之第三製程氣體之流速$ =在從10 seem(每分鐘標準立方米)到2〇 slm(每分鐘標準公升)之 範圍内，對NO氮化氣體而言為1到5〇〇〇 sccm，而對稀釋氣體而 言為 100 seem 到 20 slm。 根據本發明之一實施例，在將包含水蒸氣之第一製程氣體流 動到製程腔室12中之前’如圖1所顯示’藉由氫氣(Η〗)與氧氣(〇2) 之燃燒作用以在製程腔室12外部產生水蒸氣。如圖丨所描述，產 生第一濕製程氣體之一範例為使用Tokyo Electron Ltt MrasaH Tamanashi，Japan 所發展之高稀釋致熱炬 18 (high-dilution ’ pyrogenic torch)。高稀釋致熱炬燃燒小流量之氫氣與氧氣。致熱炬 18因此在製程腔室12外部產生水蒸氣(即蒸氣形式之水蒸氣）。 在本發明之另一實施例中，在處理環境中使用稀釋^體來稀 釋第一與第二製程氣體。稀釋氣體之濃度與第一和第二製程氣體 之濃度之比率會影響氧化石夕或氮氧化；ε夕膜之沉積速率。因此，可 201220394 以使用稀釋氣體來控制氧化矽膜生長速率與氮氧化矽臈生長速 率。在一實施例中，如圖1所顯示，稀釋氣體包含氮氣既)。然而， 可以使用其他非反應性氣體，例如：氬(Ar)。仍舊參考圖1，熟悉 本技藝者將容易地了解，可以使用氮稀釋氣體來稀釋包含水蒸^ 之第一製程氣體，而不需將：^〇氣體流動到製程腔室中。“、、、 在方法之另一實施例中，一旦氧化矽膜或氮氧化矽膜沉積在 各基板20上，便以高於沉積溫度之熱處理溫度來熱處理其上有膜 之基板20。在此技藝中眾所皆知，熱處理基板2〇上之二氧化矽戋 氮氧化矽膜會更改膜之特性，尤其是膜之電氣特性，因此會變更 含膜裝置之電氣特性。根據本發明之實施例，在熱處理期間，可 以更改處理環境與處理壓力。舉例來說，在製程腔室丨^中之膜、、冗 積作用之後’在熱處理前製程腔室12會被真空洗滌一或更多次' 以去除包含第-、第二、與非必要m氣體之處理環境以 及稀釋軋體(若有的話）。處理環境一經洗滌，熱處理氣體會被 並且處理職12时建立熱處理溫度與熱處_力，其會 沉積壓減升籍健力。或者，其上有氧切魏氧化頻之 基板20會傳送到不同處理系統以進行熱處理。熱處理壓力可以相 似於沉積壓力之翻。減-實施例，熱處戦體包含氮氣 if化巧0)^—氧化二氮既0)、氧氣(〇2)、或水田2〇)、或其混 σ物之至少一者。 圆4你顯不根據本發明實施例之為DCS流速的函數之氧 沉積速率。膜沉積條件包含1〇〇 sccm之H2氣體流速度與1〇〇 =〇2氣誠速舰過致酸18、水魏產生器，因此產生水菜 乳。使用200 seem之&稀釋氣體流速來稀釋包含水基氣之 程氣體。在氧化賴之沉積期間建立α2Τ啦之處理壓力，U ，度可以變餘45(TC到60(TC間。氧化石夕膜之厚度小 ⑶ A。DCS氣體流速可以變化於1〇 _到2〇 _ 增加⑽流速會導致增加之氧切沉積速率，在4u不 之沉積严下從約3-4 Α/min增加到約9_1〇 “、以及：6〇上 下從6A/min增加到約nA/min。此外，為了作比較，圖4顯 201220394 面上使用將DCS與N2〇反應之習知HT0製程於810°C之 ίϊΐΐ下之氧化石夕膜之沉積速率僅為約2A/min，而且沉積速率 實質上與DCS麵錢。 仪午 ^ 5係顯示根據本發明實施例之為N2後沉積熱處理溫度的函 口暫不I氧化矽膜之濕蝕刻速率。濕蝕刻速率為氧化矽膜之材料 ===量測，其中高品質氧化矽膜濕蝕刻慢於低品質氧化矽膜。 —1在Nl^體之0·5 Torr之處理壓力與不同溫度之(沉積)製程腔 ，、心儿積之氧化碎膜接著被熱處理1小時。在熱處理之後， 膜接著在稀釋呵細]，_ ··明巾經歷2.5分鐘之 if ’而且將蝕刻速率對基線™0氧化矽膜之蝕刻速率正 锕攻二基線HT〇氧化石夕膜係於800°c下使用5〇 seem之DCS氣 lOOseem之凡0氣體流速沉積而成。圖5顯示對於相同 二切膜而言’更高之_溫度或更高之DCS氣體流 =導致更南之濕侧速率。此外，後沉積熱處理溫度越高，使 沈"1之Dcs氣體流速所沉積之氧化梦膜之濕姓刻速率越 °例中’於600°c之基板溫度下使用低DCS氣體流速(10 ΓΓΪΪ賴鮮在&氣體+、之絲溫度下經熱處理之 、之濕，速率小於基線HT〇氧化石夕膜之濕侧速率。 + J，顯示藉由本發明實施綱形成之氧化賴氮氧化石夕膜 齡朗⑽與水魏纽魏化賴，並且 _之n〇氣體添加至,j㈣與水蒸氣製程 ‘合積氮，化賴。表1與圖6之結果說明n〇氣體之添 m ^ 速率、等效氧化物厚度⑽乃、以及介電常數
雖然未顯示於表1中，對於在◦到5〇 _間之NO 而吕’介面陷醉密度P顏期會減少至基線氧化石夕之介面 f, U1〇g〇(^ E12eV-cm-2E10eV-lcm-2) 〇 ^的會提T有撕地無電荷_之介面之氮氧化矽 Ϊ盘1=! 利地使用作為具有大幅改善之電子/電動遷 ”與最南通道驅動電流之金氧半導體場效電晶师⑽ET， metal 0X1de semiconductOT fleld effect 咖也㈣裝置之問介 而 9 201220394 且’當NO氣體流速增加到大於5〇 sccm，而氮氧化石夕膜中之N濃 度進一步增加時，不管Dit值之增加，預期將改善包含氮氧化矽膜 (例如：非揮發性記憶體(NVM，n〇n-V〇latilememory)應用，如快閃 記憶體隧道閘極)之半導體裝置之可靠度。雖然增加之Dit值表示介 面電荷捕獲與MOSFET起始電壓(Vth)之可能偏移之可能性提高， NVM應用之可靠度之改善被認為比因Dit增加所帶來之任何缺點 重，。增加之N濃度被認為有利於將膜内之鬆(懸浮)原子鍵結結 合得更緊密。此外，增加之N濃度會提高膜之密度，而且導致對 於在上升電壓之電子衝擊(electron b〇mbardmem)(常使用於半導體 處理期間)之阻力增加。總體而言，結果顯示，不像使用〇(：：8與 N20之先前技術反應，在使用DCS與h2〇之膜沉積期間添加 有效於將N，合至氧化石夕膜，以形成半導體裝置之氮氧化石夕膜。 、雖然已藉由其一或多個實施例之描述來說明本發明，以及雖 然^相當詳細地說明本實施例’其跡意圖將隨附申請專利範圍 限定或以任何方式限制於這些詳述。額外優點與修改將容 露給熟悉本技藝者。本個因此不限制於顯示與描述之特定^ 節、代表設備與方法、以及綱_。因此，在不般明 概念之範圍内，可以變更這些細節。 奴货月 【圖式簡單說明】 部分，闡明 面之詳細說 隨附之圖示，包含於說明書内且構成說明書的— 本發明之實施例，並且連同上述發明之一般說明盥 明，得以解釋本發明。 圖1係橫剖面圖，概略地顯示根據本發明一實施 理數個基板之批次式處理系統； j之用來處 圖圖2係在基板上沉積氧化物膜之方法之一實施例之製程流程 •圖3係在基板上沉積氮氧化物膜之方法之—實施例之製程流 之氡化矽 圖4係顯示根據本發明實施例之為DCS流速的函數 201220394 沉積速率； 齡:^ 3 ίΐΐίΤΪ據本發明實施例之為N2後沉積熱處理溫度的函 數之不同氧化矽膜之濕蝕刻速率； 圖6係藉由本發明實施例所形成之氧化矽與氮氧化矽膜之電 容-電壓曲線。 【主要元件符號說明】 10批次式處理系統 12製程腔室 13基板支撐器 14真空口 15排氣口 16、17進氣口 18致熱炬 20基板 200、300 方法 202、204、206、208、210、212 步驟 302、304、306、308、310、312、314 步驟

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  1. 201220394 七、申請專利範圍： 1. 一種在基板上形成介電膜之方法，該方法包含： 將數個基板安置在製程腔室中； . 將該製程腔室加熱至4〇〇°C與少於65〇°C間之沉n . 將包含水統U織财細該餘腔室^^又’ 氯魏之第二製程氣體流動_製程腔室中； 在該I程腔室中建立少於2 Torr之氣顏力；以及 •熱沉積 氧化ίί第一與該第二製程氣體反應，以在該數個基板上： ϋ申!利範圍第1項之在基板上形成介電膜之方法，更包含 曰燒氫氣(1¾)與氧氣(〇2)以在該製程腔室外部產生該水蒸氣。 .如申^專利範圍第1項之在基板上形成介電膜之方法，更包含， 在形成該氧化矽膜後，在熱處理氣體中熱處理其上該 Τ膜，該基板’該減理氣體包含氮邮2)、-氧化邮。)、一氧 化二氮(N2Q)、氧氣(〇2)、或水(邮）、或其混合物之至少一者。 ^申請專利範圍第3項之在基板上形成介電膜之方法，其中該 “、、处理係執行於高於該沉積溫度之溫度下。 5. 如申請專利範圍第1項之在基板上形成介電膜之方法，更包含 ^在流動該第一製程氣體與該第二製程氣體時將第一稀釋氣體 〜動到該製程腔室中，以控制該氧化矽膜之生長速率。 6. 如申請專利範圍第1項之在基板上形成介電膜之方法，更包含 在流動該第一製程氣體與該第二製程氣體時將包含一氧化氮 讲〇)氣體之第三製程氣體流動到該製程腔室中；以及 _使該氧化矽膜與該第三製程氣體反應，以在該基板上形成氮 氧化矽膜。 12 201220394 8.如利範圍第6項之在基板上形成介電膜之方法，更包含 第—製程氣體與該第二製程氣體時將第—稀釋氣體 机動到該製程腔室中，以控繼氧化石夕膜之生長速率；以及 中，時將第二稀釋氣體流動到該製程腔室 ^以控制氮結合到該氧化梦膜。 .如申請專利範圍第6項之在基板上形成介電膜之方法，更包含 在形成該氮氧化矽膜後，在熱處理氣體中熱處理盆上有該氣 氧^石夕膜之絲板’雜處理氣體包含氮氣㈣、—氧/化 一氧化二氮(Ν2〇)、氧氣(〇2)、或水(π》)、或其混合物之至少一者。 =·如申請專利範圍第9項之在基板上形成介電膜之方法 熱處理係執行於高於該沉積溫度之溫度下β 11·如申請專利範圍第6項之在基板上形成介電膜之方法，其 氮氧化矽膜具有比該氧化矽膜更低之介面陷阱密度(Dit)。’、 12· —種在基板上形成介電膜之方法，該方法包含： 將數個基板安置在製程腔室中； 將該製程腔室加熱至400°C與少於65(TC間之沉積溫度； 將包含水蒸氣之第一製程氣體流動到該製程腔室中，^中 由燃燒氫氣與氧氣以在該製程腔室外面產生該水蒸氣；9 將包含二氯石夕烧(DCS)之第二製程氣體流動到該製程腔室中. 在該製程腔室中建立少於2Torr之氣體壓力，· ’
    使該第一與該第二製程氣體反應，以在該數個基板上埶 氧化矽膜；以及 ”、、" 13 201220394 氧切膜後，在熱處理纽中熱處理其上有該氧化 = 該熱處理氣體包含氮邮2)、—氧化_〇)氧 一氮f )、氧氣(〇2)、或水既⑺、或其混合物之至少 並 中該熱處理係執行於高於該沉積溫度之溫度下。 八 如申請專利範圍第12項之在基板上形成介電膜之方法，更包 、⑼，ii該第—製程氣體與該第二製程氣體時將第-稀釋氣體 流動到該製程腔室中，以控制該氧化矽膜之生長速率。轧體 14. 一種在基板上形成介電膜之方法，該方法包含： 將數個基板安置在製程腔室中； 將該製程腔室加熱至400°C與少於650。(：間之沉積溫度； 將包含水蒸氣之第一製程氣體流動到該製程腔室中又， 將包含二氯矽烷(DCS)之第二製程氣體流動到該製程腔室 將包含一氧化氮(NO)之第三製程氣體流動到該製程腔室中； 在該製程腔室中建立少於2 Torr之氣體壓力； 使該第一、該第二、與該第三製程氣體反應，以在該數個 基板上熱沉積氮氧化矽膜；以及 在形成該氮氧化矽膜後’在熱處理氣體中熱處理其上 氧化矽膜之該基板’該熱處理氣體包含氮氣⑼2)'、一氧化氮^ 一氧化二氮恥0)、氧氣(〇2)、或水既〇)、或其混合物之至少一^ ' 15. 如申請專利範圍第14項之在基板上形成介電膜之方法，1中 該熱處理係執行於高於該沉積溫度之溫度下。' • i 16. 如申請專利範圍第14項之在基板上形成介電膜之方法， ^藉由燃燒氫氣(HO與氧氣(〇2)只在該製程腔室外面產生該水蒸I 201220394 :如申請專纖圍第14項之縣板上形成介親之方法，更包 流動ίί=;ΐ程氣體 中，峨嶋猶 將包^申二專項之在基板上形成介賴之方法，其中 1程氣體。、〜第三製程氣體在該製程腔室相添加到^第 圖式： 15
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