TW201704517A - 藉由原子層沉積及原子層蝕刻的保形膜之沉積 - Google Patents

藉由原子層沉積及原子層蝕刻的保形膜之沉積 Download PDF

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TW201704517A
TW201704517A TW105109955A TW105109955A TW201704517A TW 201704517 A TW201704517 A TW 201704517A TW 105109955 A TW105109955 A TW 105109955A TW 105109955 A TW105109955 A TW 105109955A TW 201704517 A TW201704517 A TW 201704517A
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substrate
processing
chamber
precursor
etchant
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TW105109955A
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TWI706049B (zh
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米歇爾 丹納克
強 亨利
沙恩 唐
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蘭姆研究公司
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    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract

提出一種在原子層沉積期間使用含鹵素蝕刻劑以沉積保形膜之方法。該方法涉及，在使基板暴露至第一前驅物與使基板暴露至第二電漿活化反應物之間使基板暴露至含鹵素蝕刻劑，例如三氟化氮。可沉積之保形膜之範例包括含矽膜及含金屬膜。亦提出相關的設備。

Description

藉由原子層沉積及原子層蝕刻的保形膜之沉積
本發明係關於藉由原子層沉積及原子層蝕刻的保形膜之沉積。
元件（例如半導體元件）之製造可能涉及，在基板上之凸起或凹陷特徵部之中或之上沉積各種介電膜、導電膜或半導體膜。對基板之下方形貌為保形的膜沉積可能是具有挑戰性的，特別是隨著特徵部之深寬比之增加及關鍵尺寸之減少。
可使用在元件製造中之膜之一範例為矽氮化物（SiN）。矽氮化物薄膜具有獨特的物理、化學及機械性質，因而使用在各種應用中。對於半導體元件而言，例如，SiN膜可使用在擴散阻障物、閘極絕緣體、側壁間隔物、封裝層、在電晶體中之著色膜、及類似者。當使用於在高深寬比特徵部中沉積SiN膜時，習知方法可能產生突出部分。當元件尺寸持續縮小時，在高深寬比特徵部中沉積保形SiN膜及其它類型的膜之需求逐漸增加。
本文中提出用於處理基板之方法及設備。一態樣係關於在腔室中處理基板之方法，該方法包含：(a) 提供具有一或更多特徵部之一基板，每一特徵部包含一特徵部開口；(b) 在容許一含矽前驅物吸附至該基板之表面上之條件下，使該基板暴露至該含矽前驅物，藉此形成該含矽前驅物之一吸附層；(c) 在使該基板暴露至該含矽前驅物之後，使該基板暴露至一含鹵素蝕刻劑；及(d) 使該基板暴露至一含氮反應物及點燃電漿，以選擇性地蝕刻在該等特徵部開口或附近之該含矽前驅物之該吸附層，及形成一矽氮化物膜。
在容許該含鹵素蝕刻劑選擇性吸附至該含矽前驅物之該吸附層上之條件下，可使該基板暴露至該含鹵素蝕刻劑。該含鹵素蝕刻劑之範例包含三氟化氮、氯、三氟甲烷、四氟化碳、及其組合。在某些實施例中，該含鹵素蝕刻劑為具有化學式Cn F2n+2 或Cn F2n 之化合物，其中n ＞ 1。
在某些實施例中，在使該基板暴露至該含鹵素蝕刻劑之後，吹淨該腔室。藉由使一吹淨氣體流動，可吹淨該腔室，該吹淨氣體例如為氬、氦、氮、及氫。
含矽前驅物之範例為甲矽烷、二矽烷、三矽烷、四矽烷、三矽基胺、胺基矽烷、及鹵代矽烷。含氮反應物之範例為氮、氨、聯胺、及胺。
在某些實施例中，該方法包含重複步驟 (a)–(d)。在某些實施例中，在同一腔室中執行步驟 (a)–(d)。
另一態樣係關於在腔室中處理基板之方法，該方法包含：藉由執行一或更多循環以沉積一膜，一循環包含：(a) 提供具有一或更多特徵部之一基板，每一特徵部包含一特徵部開口；(b) 在容許一第一前驅物吸附至該基板之表面上之條件下，使該基板暴露至該第一前驅物，藉此形成該第一前驅物之一吸附層；(c) 在使該基板暴露至該第一前驅物之後，使該基板暴露至一含鹵素蝕刻劑；及 (d) 使該基板暴露至一第二反應物及點燃電漿，以選擇性地蝕刻在該等特徵部開口或附近之該第一前驅物之該吸附層，及形成一膜。
含鹵素蝕刻劑之範例包含三氟化氮、氯、三氟甲烷、四氟化碳、及其組合。在某些實施例中，含鹵素蝕刻劑為具有化學式Cn F2n+2 或Cn F2n 之化合物，其中n ＞ 1。
在各種實施例中，在步驟 (d) 之前，吹淨該腔室。該膜可為，例如，介電膜或金屬膜。在某些實施例中，該膜為含矽膜，例如矽氮化物、矽碳化物、或矽氧化物。該第二反應物可為氧化劑或還原劑。在各種實施例中，每n個循環執行步驟 (d)，其中n係等於或大於1之整數。
另一態樣係關於一種處理基板之設備，該設備包含：(a) 至少一處理腔室，該處理腔室包含一基座，用以支托一基板；(b) 至少一出口，用以連接至一真空；(c) 一或更多處理氣體入口，連接至一或更多含矽前驅物源及一或更多含鹵素蝕刻劑；(d) 一射頻（RF）產生器；及 (e) 一控制器，用以控制在該設備中之操作，該控制器包含複數機器可讀指令，該等機器可讀指令係用於：(i) 引入一含矽前驅物至一處理腔室；(ii) 在引入該含矽前驅物之後，引入一含鹵素蝕刻劑至該腔室；及 (iii) 引入一含氮反應物至該腔室及點燃電漿，以形成一矽氮化物膜。
該控制器可更包含用於在引入該含氮反應物之前、引入一吹淨氣體以吹淨該腔室之機器可讀指令。
含鹵素蝕刻劑之範例包含三氟化氮、氯、三氟甲烷、四氟化碳、及其組合。在某些實施例中，含鹵素蝕刻劑為具有化學式Cn F2n+2 或Cn F2n 之化合物，其中n ＞ 1。
再另一態樣係關於一種處理基板之設備，該設備包含：(a) 至少一處理腔室，該處理腔室包含一基座，用以支托一基板；(b) 至少一出口，用以連接至一真空；(c) 一或更多處理氣體入口，連接至一或更多前驅物源及一或更多含鹵素蝕刻劑；(d) 一射頻（RF）產生器；及(e) 一控制器，用以控制在該設備中之操作，該控制器包含複數機器可讀指令，該等機器可讀指令係用於：(i) 引入一前驅物至一處理腔室；(ii) 在引入該前驅物之後，引入一含鹵素蝕刻劑至該腔室；及(iii) 引入一第二反應物至該腔室及點燃電漿，以形成一膜。
這些及其它態樣將參考著圖式而進一步說明如下。
在以下敘述中，數個特定細節被提出以提供對於所呈現的實施例之徹底了解。所揭露的實施例可在沒有這些特定細節之部分或全部之情況下加以實施。在其它的情況下，熟知的處理操作並未詳細地描述以免不必要地混淆所揭露的實施例。雖然所揭露的實施例將結合特定實施例而加以敘述，但應當了解，其並非用來限制所揭露的實施例。
以下所揭露的實行例描述材料沉積在基板（例如，晶圓或其它工作件）上。工作件可具有各種形狀、尺寸及材料。除了半導體晶圓，可使用在本文所揭露的實行例之其它工作件包括各種物品，例如印刷電路板及類似物。處理及設備可使用在半導體元件、顯示器、LED、太陽光電板及類似物之製造中。
在一範例中，矽氮化物可使用在半導體元件製造中以做為擴散阻障物、閘極絕緣體、側壁間隔物及封裝層。在一特定應用中，矽氮化物係使用做為在記憶元件中之記憶體封裝層。在這樣的元件中，碳層可沉積在受熱時發生相改變之相變化層上。當受損時，相變化層未必進行相變。相變化層亦可對光敏感。為防止對相變化層的任何損壞，可在相變化層上沉積矽氮化物保形記憶體封裝層。記憶體封裝層有少量乃至沒有其它化合物之污染，並且在低溫下進行沉積以避免損壞元件。保形矽氮化物層亦可使用在其它應用中。
本文中所提出的是，藉由混合原子層蝕刻（ALE）技術及原子層沉積（ALD）而沉積保形膜之方法。所揭露的實施例包括沉積矽氮化物之方法，其形成含矽前驅物之吸附層，含矽前驅物之吸附層具有足夠的反應性以與含氮電漿起反應。應當注意，雖然本文中所提出的範例描述矽氮化物之保形沉積，但應當了解，可使用所揭露的實施例以沉積其它材料。例如，本文中所提出之方法可用於在元件製造中沉積矽氧化物、矽碳化物、摻雜的含矽膜、含金屬膜（例如鋁氮化物及鈦氮化物）、及其它保形膜。
所沉積的膜為保形的。膜的保形性（conformality）可藉由階梯覆蓋率而加以量測。階梯覆蓋率可藉由將特徵部之底部、側壁、或頂部上之沉積膜的平均厚度與特徵部之底部、側壁、或頂部上之沉積膜的平均厚度進行比對而加以計算。例如，階梯覆蓋率之計算可藉由將側壁上之沉積膜的平均厚度除以特徵部之頂部之沉積膜的平均厚度、並且將其乘以100以得到百分比。某些所揭露的實施例涉及將保形層沉積在基板上，其係藉由在原子層沉積循環期間，在使基板暴露至前驅物與使基板暴露至第二反應物（在電漿環境中）之間，使基板暴露至蝕刻劑。
本文中所提出的方法涉及，藉由混合某些ALE技術及ALD之膜沉積。ALE為使用相繼的自限制反應而移除材料薄層之技術。通常，ALE循環包括改質操作，以形成反應性層；接著是移除操作，以僅僅移除或蝕刻此已改質的層。做為一範例，ALE循環可包括下列操作：（i）輸送反應物氣體至容納基板之腔室；（ii）從腔室吹淨反應物氣體；（iii）輸送移除氣體及可選的電漿；及（iv）吹淨腔室。
ALD為使用相繼的自限制反應而沉積材料薄層的技術。通常，ALD循環包括下列操作：將至少一反應物輸送及吸附至基板表面；接著使吸附的反應物與一或更多反應物進行反應，以形成部分的膜層。做為一範例，矽氮化物沉積循環可包括下列操作：（i）輸送∕吸附含矽前驅物；（ii）從腔室吹淨含矽前驅物；（iii）輸送氮電漿；及（iv）從腔室吹淨電漿。可使用各種前驅物及共反應物之脈衝以沉積其它種類的膜。
不像化學氣相沉積（CVD）技術，ALD處理使用表面媒介沉積反應以逐層地沉積膜。在ALD處理之一範例中，使包含一群表面活性位置之基板表面暴露至第一前驅物（例如，含矽前驅物）之氣相分佈區域，第一前驅物以注入之方式被提供至容納基板之腔室。此第一前驅物之分子被吸附在基板表面上，包含第一前驅物之化學吸附的物種、及∕或物理吸附的分子。應當了解，當化合物被吸附至基板表面上時（如本文所述），吸附層可包含化合物、以及化合物之衍生物。例如，含矽前驅物之吸附層可包括含矽前驅物、以及含矽前驅物之衍生物。在第一前驅物注入之後，接著排空腔室以移除維持於氣相之第一前驅物之大部分或全部，以僅僅留下吸附的物種。在某些實行例中，可能不完全排空腔室。例如，可排空反應器，俾使氣相之第一前驅物之分壓為足夠低以降低反應。將第二反應物（例如含氮反應物）導入至腔室，俾使該等分子之某些與吸附在表面上之第一前驅物進行反應。在某些處理中，第二前驅物立即與吸附的第一前驅物進行反應。在其它實施例中，第二前驅物僅在暫時地施加活化源之後才進行反應。接著可再度排空腔室，以移除未結合的第二反應物分子。如上所述，在某些實施例中，可能不完全排空腔室。額外的ALD循環可用於增加膜厚。
在某些實施例中，ALD第一前驅物之注入使基板表面部分地飽和。在某些實施例中，ALD循環之注入階段在前驅物接觸基板之前結束，以平均地使表面飽和。通常，在此時，前驅物流動被關閉或轉向，且只有吹淨氣體流動。藉由在此次飽和狀態下進行操作，ALD處理降低循環時間，並且增加產量。然而，因為前驅物吸附不是飽和受限的，所以吸附的前驅物之濃度可能在基板表面各處稍有變化。在次飽和狀態下操作之ALD處理之範例係提供於：申請日為2013年10月23日、且名稱為“SUB‑SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION＂之美國專利申請案第14/061,587號，其整體內容併入於本文中作為參考。
在某些實施例中，ALD方法包括電漿活化。如本文所述， 本文中所描述之ALD方法及設備可為保型膜沉積（CFD）方法，其大致上描述於：美國專利申請案第 13/084,399號（現為美國專利第 8,728,956號），申請日為 2011年4月11日、且名稱為“PLASMA ACTIVATED CONFORMAL FILM DEPOSITION＂；以及美國專利申請案第13/084,305號，申請日為 2011年4月11日、且名稱為“SILICON NITRIDE FILMS AND METHODS＂，其整體內容併入於本文中作為參考。
圖1為處理流程圖之範例，描繪用以執行根據所揭露的實施例之方法之操作。雖然本文中所提出之範例是在沉積矽氮化物膜之背景下描述所揭露的實施例，但應當了解，亦可使用方法以藉由ALD而沉積任何的材料膜。
在圖1之操作101中，將基板提供至單站或多站腔室之處理站。該基板可為矽晶圓，例如200 mm晶圓、300 mm晶圓、或450 mm晶圓，包括具有一或更多材料（例如介電材料、導電材料、或半導體材料）層沉積於其上之晶圓。基板可具有“特徵部＂，例如介層窗或接觸窗孔洞，其特徵在於下列之一或更多者：狹窄及∕或內凹角開口、在特徵部中之收縮部、及高深寬比。特徵部可形成在上述層之一或更多者中。特徵部之一範例為在半導體基板或基板上之層中之孔洞或介層窗。另一範例為在基板或層中之溝渠。在各種實施例中，該特徵部可具有下方層，例如阻障層或黏著層。下方層之非限制性範例包括介電層及導電層，例如矽氧化物、矽氮化物、矽碳化物、金屬氧化物、金屬氮化物、金屬碳化物、及金屬層。
在某些實施例中，特徵部可具有至少約2：1、至少約4：1、至少約6：1、至少約10：1、至少約30：1、或更高之深寬比。特徵部亦可具有接近開口之尺寸，例如在約10 nm至500 nm之間（例如在約25 nm與約300 nm之間）之開口直徑或線寬。所揭露的方法可在具有特徵部（特徵部之開口小於約150 nm）之基板上加以執行。介層窗、溝渠或其它凹陷特徵部可稱為未填充特徵部或特徵部。根據各種實施例，特徵部輪廓可能逐漸縮小及∕或在特徵部開口包含突出部分。內凹角（re-entrant）輪廓為自特徵部之底部、封閉端、或內部縮小至特徵部開口之輪廓。內凹角輪廓可能由在圖案化期間之不對稱蝕刻動力學、及∕或由於在先前膜沉積（例如擴散阻障物之沉積）中之非保形膜階梯覆蓋之突出部分所造成。在各種實施例中，特徵部之頂部之開口寬度可能小於特徵部之底部之寬度。
在圖1之操作103-115期間，可使惰性氣體流動。在各種實施例中，使用惰性氣體做為載氣。示例性載氣包含氬、氦及氖。在某些實施例中，載氣不是氫，俾使所沉積的矽氮化物膜係包含少量氫至不含氫。在某些實施例中，可使用含氫載氣。在某些實施例中，在某些操作中使用載氣做為吹淨氣體。在某些實施例中，載氣被轉向。可提供惰性氣體，以協助處理腔室之壓力及∕或溫度控制、液體反應物之汽化、較快的反應物傳送及∕或做為用於自處理腔室及∕或處理腔室管路將處理氣體移除之清掃氣體。
各種所揭露的實施例可在約0.1 Torr與約20 Torr之間之壓力下加以執行。在許多實施例中，所揭露的方法可在小於約650 °C、或小於約450 °C、或在約50 °C與約650 °C之間（例如約200 °C）之基板溫度下加以執行。在這樣的實施例中，基座可設定為小於約450 °C之溫度，以控制基板溫度。在某些實施例中，方法係在較高的溫度下加以執行，例如大於約250 °C、或大於450 °C。
在圖1之操作103中，使基板暴露至第一前驅物，俾使第一前驅物吸附至基板表面上。雖然本文中提出之範例使用含矽前驅物做為第一前驅物，但應當了解，第一前驅物可為任何適合的前驅物以用於在基板上沉積膜，例如，矽氮化物、矽氧化物、矽碳化物、鋁氮化物、鎢氮化物、鈦氮化物、鉭氮化物、鈦氧化物、及其它的膜。
操作103可為ALD循環之一部分。如前文之討論，一般而言，ALD循環為用以執行一次表面沉積反應之最小操作組。在某些實施例中，一循環之結果係在基板表面上產生至少部份的矽氮化物膜層。循環可包含某些輔助操作，例如掃除反應物或副產物其中一者、及∕或對所沉積的部分膜進行處理。一般而言，一循環包含獨特操作序列之一情況。如前文之討論，一般而言，一循環為用以執行一次表面沉積反應之最小操作組。一循環之結果係在基板表面上產生至少部份的膜層，例如部份的矽氮化物膜層。
在操作103期間，使基板暴露至第一前驅物，俾使第一前驅物吸附至基板表面上以形成吸附層。在某些實施例中，含矽前驅物以自限制的方式吸附至基板表面上，俾使活性位置一旦被含矽前驅物佔據，則少量或沒有額外的含矽前驅物將被吸附在基板表面上。例如，含矽前驅物可吸附至約60%的基板表面上。在各種實施例中，當含矽前驅物流動至腔室時，含矽前驅物吸附至基板表面上之活性位置上，形成含矽前驅物薄層在表面上。在各種實施例中，此層可小於單分子層，並且可具有約0.2Å與約0.4Å之間之厚度。本文中所提出之方法可在低於約450 °C之溫度加以執行。在大於約450 °C之處理溫度下，某些含矽前驅物可能分解而形成一層矽。
含矽前驅物為用於製造含矽膜之單一試劑或試劑混合物，其中該試劑或試劑混合物包含至少一矽化合物。在某些實施例中，含矽前驅物可為，例如，矽烷、鹵代矽烷、或胺基矽烷。然而，在各種實施例中，含矽前驅物為不含鹵素。不含鹵素的矽烷可包含氫及∕或碳基，但不包含鹵素。
根據所揭露的實施例，適合使用之含矽前驅物包含：聚矽烷（H3 Si- (SiH2 )n -SiH3 ），其中n ≥ 0。矽烷之範例為甲矽烷（SiH4 ）、二矽烷（Si2 H6 ）、以及有機矽烷，例如甲基矽烷、乙基矽烷、 異丙基矽烷、三級丁基矽烷、二甲基矽烷、二乙基矽烷、雙-三級丁基矽烷、丙烯基矽烷、二級丁基矽烷、 叔己基矽烷、異戊基矽烷、三級丁基二矽烷、雙-三級丁基二矽烷、及類似者。
鹵代矽烷包含至少一鹵基並且可能或可能不包含氫及∕或碳基。鹵代矽烷之範例為碘矽烷、溴矽烷、氯矽烷、及氟矽烷。雖然鹵代矽烷（尤其是氟矽烷）在電漿點燃時可能形成會蝕刻矽材料之反應性鹵化物物種，但在某些實施例中，鹵代矽烷在電漿點燃時可能未引入腔室中，所以可能減少來自鹵代矽烷之反應性鹵化物物種之形成。特定的氯矽烷為四氯矽烷、三氯矽烷、二氯矽烷、單氯矽烷、氯丙烯基矽烷、氯甲基矽烷、二氯甲基矽烷、氯二甲基矽烷、氯乙基矽烷、三級丁基氯矽烷、雙-三級丁基氯矽烷、氯異丙基矽烷、氯-二級丁基矽烷、三級丁基二甲基氯矽烷、叔己基二甲基氯矽烷、及類似者。
胺基矽烷包含鍵結於一矽原子之至少一氮原子，但也可包含氫、氧、鹵素及碳。胺基矽烷之範例為單、雙、三及四-胺基矽烷（分別為H3 Si(NH2 )4 、H2 Si(NH2 )2 、HSi(NH2 )3 及Si(NH2 )4 ），以及受取代的單、雙、三及四-胺基矽烷，例如三級丁基胺基矽烷、甲基胺基矽烷、三級丁基矽烷胺、雙(三級丁基胺基)矽烷（SiH2 (NHC(CH3 )3 )2 ，BTBAS）、三級丁基矽基胺甲酸酯、SiH(CH3 )-(N(CH3 )2 )2 、SiHCl-(N(CH3 )2 )2 、(Si(CH3 )2 NH)3 、及類似者。胺基矽烷之進一步範例為三矽基胺（N(SiH3 ) ）。
可用來在操作103中替代含矽前驅物之其它第一前驅物之範例將提出如下。
圖2A及2B為概要表示圖，顯示根據圖1之方法中之各種階段之範例。圖2A及2B顯示在基板表面上之複數分子之範例，該等分子在特徵部開口或附近，其可能在特徵部之頂部或附近。在某些實施例中，在特徵部中、延著該特徵部之側壁或底部之基板表面可能顯現如圖2A及2B所繪示之化學機制。在圖2A及2B所提出之範例中，含矽前驅物為二矽烷，蝕刻劑為三氟化氮，第二反應物為氮。應當了解，在所揭露的實施例中可使用其它含矽前驅物、蝕刻劑及第二反應物，且在某些實施例中，可能遭受類似於圖2A及2B所繪示之化學機制。
在圖2A之201中，使基板200暴露至二矽烷，藉此二矽烷分子211、221、231吸附至基板200之表面上，形成二矽烷吸附層。
返回至圖1，在操作105中，可選地使處理腔室進行吹淨，以移除沒有吸附在基板表面上、處於氣相的過量含矽前驅物。吹淨腔室可涉及使吹淨氣體（purge gas）或清掃氣體流動，吹淨氣體或清掃氣體可為使用在其它操作中之載氣或可為不同的氣體。在某些實施例中，吹淨可涉及排空腔室。示例性吹淨氣體包含氬、氮、氫及氦。在某些實施例中，操作105可包含用以排空處理腔室之一或更多排空子階段。或者，應當理解，在某些實施例中，可省略操作105。操作105可具有任何適當的持續時間，例如在約0秒與約60秒之間，例如約0.01秒。在某些實施例中，增加一或更多吹淨氣體之流率可減少操作105之持續時間。例如，可根據處理腔室及∕或處理腔室管路的各種反應物熱力學特性及∕或幾何特性而調整吹淨氣體流率，以修改操作105之持續時間。在一非限制性範例中，可藉由調整吹淨氣體之流率而調整吹淨階段之持續時間。此可減少沉積循環時間，因而改善基板產量。在吹淨之後，含矽前驅物保持吸附在基板表面上。
在操作107中，使基板暴露至含鹵素蝕刻劑。含鹵素蝕刻劑可為任何含鹵素化合物，例如含氟化合物或含氯化合物。在各種實施例中，含鹵素蝕刻劑為三氟化氮、氯、或含碳蝕刻劑、或其組合。在某些實施例中，含碳蝕刻劑為CHF3 、或具有Cn F2n+2 或Cn F2n 之化學式之化合物，其中n ＞ 1，例如CF4 。在執行ALD以沉積氮化物之某些實施例中，可能避免含氯蝕刻劑化合物。這是因為含氯蝕刻劑化合物通常無法輕易地蝕刻氮化物。
執行操作107之頻率可取決於由所沉積的ALD層所觀察到的突出部分之量。在各種實施例中，每1至每50循環之ALD，執行操作107。在某些實施例中，在每一循環之ALD中，執行操作107。在某些實施例中，每50或更多循環之ALD，執行操作107。可在非電漿環境中執行操作107。在電漿環境中執行操作107可能產生大量的反應性鹵化物物種，因此在基板上蝕刻超出預期。例如，反應性鹵化物物種可能蝕刻在基板表面上之大部分或全部的吸附的第一前驅物，因而降低產量及減少沉積速率。
不受限於特定理論，含鹵素化合物吸附在含矽前驅物之吸附層之表面上。例如，在圖2之203中，三氟化氮分子243吸附在基板200上之二矽烷吸附層上。在許多實施例中，使含鹵素蝕刻劑流入腔室中一持續時間，該持續時間足以吸附在大部分或全部的基板表面上。在某些實施例中，含鹵素蝕刻劑可選擇性地吸附在特徵部開口或附近。在某些實施例中，含鹵素蝕刻劑可選擇性地吸附，俾使在特徵部開口附近，含鹵素蝕刻劑吸附在特徵部（例如垂直特徵部）之頂部或附近比吸附在特徵部之底部或附近更多。有助於在特徵部之頂部或附近之選擇性吸附之適當處理條件係描述於下。
返回至圖1，在操作109中，吹淨處理腔室，以移除殘留的蝕刻劑，例如以氣相餘留、且未吸附在第一前驅物吸附層之表面上之蝕刻劑。吹淨條件及方法可為關於操作105所述之任何一者。在某些實施例中，執行操作109，以在後續的操作中，防止殘留的蝕刻劑去移除太多的第一前驅物吸附層。例如，若殘留的三氟化氮氣體出現在腔室中且同時點燃電漿，則受激發的氟可能撞擊基板，因而蝕刻基板之表面，導致蝕刻之執行多於沉積。在某些實施例中，若電漿點燃時，氣相的殘留蝕刻劑在腔室中，則沉積之效率及沉積速率可能降低。
在操作111中，使基板暴露至第二反應物及點燃電漿。在各種實施例中，可在相同的時間打開第二反應物流動及電漿。在某些實施例中，可在打開電漿之前打開第二反應物流動，例如，以穩定第二反應物流動。在各種實施例中，第二反應物為含氮反應物，以形成至少一部分矽氮化物膜在基板表面上。含氮反應物為包含至少一氮之一反應物或複數反應物之混合物，例如，氨、聯胺、胺（帶有碳的胺），例如甲基胺、二甲基胺、乙基胺、異丙基胺、三級丁基胺、雙-三級丁基胺、環丙基胺、二級丁基胺、環丁基胺、異戊基胺、2-甲基丁基-2-胺、三甲基胺、二異丙基胺、二乙基異丙基胺、雙-三級丁基聯胺、以及芳族胺，例如苯胺、吡啶、及芐胺。胺可為一級胺、二級胺、三級胺、或四級銨（例如，四烷基銨化合物）。含氮反應物可包含氮以外之雜原子，例如，羥基胺、三級丁氧羰基胺、及正三級丁基羥基胺為含氮反應物。示例性含氮反應物包含氮氣、氨及胺。
為了沉積其它含矽材料，可使用其它反應物做為第二反應物以沉積不同材料之膜。例如，為了使用所揭露的實施例以沉積矽碳化物膜，第二反應物可為含碳反應物。例如，為了沉積矽氧化物，可使用氧化劑或含氧化合物。為了沉積摻雜膜，亦可加入摻質做為第二反應物。應注意，“第二反應物＂一詞可用於描述當在ALD循環中點燃電漿時被引入腔室之一或更多氣體。
在各種實施例中，在操作111期間，提供電漿能量，以使第二反應物（例如，含氮氣體）活化為離子及自由基及其它活化物種，其與第一前驅物之吸附層進行反應。例如，電漿可直接或間接地使含氮氣相分子活化，以形成氮自由基或離子。電漿亦可激發吸附的蝕刻劑，從而形成激發的蝕刻劑物種，其可蝕刻第一前驅物以及從基板移除它。可監控腔室之條件，俾使足夠的蝕刻劑被激發以量身打造特徵部輪廓及改善保形性。例如，可控制電漿條件，以優先在特徵部開口或附近進行蝕刻，同時形成較少的激發的蝕刻劑在側壁或附近或朝向特徵部之底部。有助於在特徵部之頂部或附近之選擇性吸附之適當處理條件係描述於下。
在各種實施例中，電漿係原位（in-situ）電漿，俾使電漿直接形成在腔室中之基板表面之上。可以約0.2122 W/cm2 與約2.122 W/cm2 之間之每基板面積之功率以點燃原位電漿。例如，對處理四個300 mm晶圓之腔室而言，功率可在約150 W至約6000 W之範圍中、或在約600 W至約6000 W之範圍中、或在約800 W至約4000 W之範圍中。舉例而言，ALD處理之電漿可藉由使用兩個電容式耦合板以施加射頻（RF）場至氣體而產生。在該等板之間藉由RF場之氣體離子化而點燃電漿，因而在電漿放電區中產生自由電子。這些電子係藉由RF場而加速，且可與氣相反應物分子發生碰撞。這些電子與反應物分子之碰撞可形成參與沉積處理之自由基物種。應當了解，RF場可經由任何適當的電極而耦合。在各種實施例中，使用具有至少約13.56 MHz、或至少約27 MHz、或至少約40 MHz、或至少約60 MHz之頻率之高頻電漿。在某些實施例中，可使用基於微波之電漿。電極之非限制性範例包含處理氣體分佈噴淋頭及基板支撐基座。應當了解，ALD處理之電漿可藉由，除了使RF場電容耦合至氣體之外，一或更多適當的方法而形成。在某些實施例中，電漿為遠端電漿，俾能在腔室上游處之遠端電漿產生器中將第二反應物點燃，然後傳送至基板所在之腔室。
處理條件係經過周密的設計，以藉由選擇性蝕刻而獲得保形膜。適當的蝕刻溫度、蝕刻劑流動、吹淨操作、電漿條件及蝕刻壓力之結合可協助達成想要的保形性。若蝕刻保形性並未對於每一類型的待沉積膜加以適當調整，則可能產生階梯覆蓋率不良之非保形沉積。處理條件為使非保形蝕刻（亦稱為選擇性蝕刻）得以執行。
在較高的溫度下，進入的蝕刻劑物種，例如氟原子，很快地在特徵部入口處進行反應及蝕刻，產生較非保形的蝕刻；在較低的溫度下，進入的蝕刻劑物種能夠進一步在特徵部中進行擴散及蝕刻，產生較保形的蝕刻。在操作109期間之較短的吹淨留下較多的蝕刻劑物種在腔室中及在基板上，造成較多的蝕刻劑物種進一步在特徵部中進行擴散及蝕刻。在操作107期間之較短的蝕刻劑暴露將傾向於在特徵部入口處進行反應及蝕刻，產生較保形的蝕刻。在某些例子中，蝕刻劑在操作107中流動，俾使含鹵素蝕刻劑優先吸附在特徵部之頂部或附近，在操作111期間，當電漿點燃時，特徵部之頂部之蝕刻多於特徵部之側壁。較低的蝕刻劑流率將產生較少的蝕刻劑分子吸附在基板表面上。較高的壓力將造成較多的蝕刻劑物種之再結合，例如氟自由基之再結合而形成分子氟。分子氟之黏附係數低於氟自由基，所以易於在蝕刻之前擴散至特徵部中，導致較不保形的蝕刻。
如圖2A所示，在205期間，基板200係暴露至第二反應物（在此例中，氮），同時電漿點燃，藉此產生激發的氮物種260，其可包含（除了別的物種之外）離子、自由基（例如，如205中所示之•N）、及中性物種。在所提出之範例中，電漿亦激發吸附的三氟化氮，其接著解離成激發的氮•N及激發的氟物種250（例如•F）。某些氟物種250可能藉由攻擊二矽烷之矽中心而與吸附的二矽烷進行反應，而某些激發的氮物種260（不論來自三氟化氮或氮）藉由攻擊二矽烷之矽中心而與吸附的二矽烷進行反應。
結果，在圖2B之207中，激發的氟與二矽烷起反應而從基板200之表面蝕刻二矽烷，並且形成六氟二矽烷（217及227），藉此，氟255現在是鍵結至矽。同時，激發的氮與在基板表面上之二矽烷起反應，Si-N鍵可形成（265），藉此形成至少一部分的矽氮化物（237）層在表面上。應當注意，在某些實施例中，蝕刻處理可能經歷不同的機制，在207中所繪示之機制為可能機制之一例。
返回至圖1，在操作113中，可選地吹淨處理腔室，以移除被蝕刻物種及任何殘留的副產物。如圖2B所示，在209中，在吹淨腔室之後，部分的矽氮化物237層留存在基板200之表面上。應當注意，雖然吸附的二矽烷層在201中覆蓋較多表面區域，但由於來自蝕刻劑三氟化氮之部分蝕刻，所以只有部分的矽氮化物沉積，如在209中所示。在每一循環期間，相較於在特徵部或溝渠之底部附近之特徵部之表面，在特徵部開口或附近之特徵部之表面可能沉積較小分率之部分的矽氮化物層。因此，可量身打造在特徵部開口或附近之沉積，且整個沉積是高度保形的。
在圖1之操作115中，判定是否已沉積想要的厚度之膜。若沒有，則重複操作103-113足夠的循環以沉積想要的厚度之膜。任何適當數量之沉積循環可包含在ALD處理中，以沉積想要的膜厚之矽氮化物。例如，可執行約50個沉積循環，以使用所揭露的實施例而沉積膜在基板上。如上所注意，操作107可能或可能不在每一沉積循環中執行。
圖3為時序圖，顯示根據所揭露的實施例之示例性脈衝。圖3顯示，示例性ALD處理300中之複數階段之各種處理參數，例如，載氣流動、第一前驅物流動、蝕刻劑流動、電漿、及第二反應物流動。該等線顯示打開及關閉流動或電漿的時間。示例性處理參數包含，但不限於，惰性及反應物物種之流率、電漿功率及頻率、基板溫度、及處理腔室壓力。描繪兩個沉積循環310A及310B。每一沉積循環包含各種階段。例如，沉積循環310A包含第一前驅物暴露階段320A、吹淨階段340A（其可為選擇性的）、蝕刻劑階段350A、吹淨階段355A、第二反應物與電漿暴露階段360A、及另一可選的吹淨階段380A。類似地，沉積循環310B包含第一前驅物暴露階段320B、吹淨階段340B（其可為選擇性的）、蝕刻劑階段350B、吹淨階段355B、第二反應物與電漿暴露階段360B、及另一可選的吹淨階段380B。如所示，在示例性處理300中，載氣在整個處理中流動。在各種實施例中，載氣被使用做為吹淨氣體。應當注意，在某些實施例中，載氣可不同於吹淨氣體。在某些實施例中，載氣僅在吹淨階段（例如，340A、355A、380A、340B、355B及380B）期間流動。載氣可為關於圖1之操作105之上述那些其中任何一者。
在第一前驅物暴露階段（320A及320B）中，第一前驅物是打開的，沒有蝕刻劑，沒有電漿，且沒有第二反應物。此階段可對應至圖1之操作103。在吹淨階段340A，其可對應至圖1之操作105，載氣流動，而第一前驅物、蝕刻劑、電漿及第二反應物是關閉的。在蝕刻劑階段350，其可對應至圖1之操作107，蝕刻劑與載氣流動，而第一前驅物、電漿及第二反應物是關閉的。在吹淨階段355A，其可對應至圖1之操作109，載氣流動，而第一前驅物、蝕刻劑、電漿及第二反應物是關閉的。在第二反應物與電漿暴露階段360A，電漿是打開的，第二反應物與載氣流動，而第一前驅物及蝕刻劑流動是關閉的。在吹淨階段380A，其可對應至圖1之操作113，載氣流動，而第一前驅物、蝕刻劑、電漿及第二反應物是關閉的。在示例性處理300中，在圖1之操作115中，判定所沉積的膜並非適當的厚度或想要的厚度，所以重複沉積循環（如310B所示）。
在某些實施例中，可僅僅在許多沉積循環（不含蝕刻劑階段）已經執行之後，才執行包含蝕刻劑階段之沉積循環。例如，可在約50個沉積循環（不含蝕刻劑階段）之後，執行包含蝕刻劑階段之沉積循環。
如上所注意，雖然本文中提出之範例係沉積矽氮化物膜，但可使用所揭露的實施例以沉積其它材料膜。例如，所沉積的膜可包含金屬。可形成之含金屬膜之範例包含鋁、鈦、鉿、鉭、鎢、錳、鎂、鍶等之氧化物及氮化物、以及元素金屬膜。示例性前驅物可包含金屬烷基胺、金屬烷氧化物、金屬烷醯胺、金屬鹵化物、金屬β-二酮、金屬羰基化合物、有機金屬、等。適當的含金屬前驅物將包含想要併入膜中之金屬。例如，可藉由五(二甲基醯胺基)鉭與氨或其它還原劑之反應而沉積含鉭層。可使用之含金屬前驅物之進一步範例包含三甲基鋁、四乙氧基鈦、四(二甲基醯胺基)鈦、四(乙基甲基醯胺基)鉿、二(環戊二烯基)錳、及二(正丙基環戊二烯基)鎂。用於沉積氧化物之示例性第二反應物包含氧化劑，氧化劑可為氧與弱氧化劑之混合物，弱氧化劑為，例如，一氧化二氮、一氧化碳、二氧化碳、一氧化氮、二氧化氮、氧化硫、二氧化硫、含氧烴（例如，Cx Hy Oz ）、及∕或水。在其它實行例中，氧化反應物可完全為弱氧化劑。或者，氧化反應物可包含臭氧。設備
圖4描繪原子層沉積（ALD）處理站400之實施例之概要圖， ALD處理站400具有用以維持低壓環境之處理腔室體402。複數ALD處理站400可包含於常見的低壓處理工具環境中。例如，圖5描繪多站處理工具500之實施例。在某些實施例中，ALD處理站400之一或更多硬體參數（包含以下詳加討論的參數）可藉由一或更多電腦控制器450而程式化地加以調整。
ALD處理站400與反應物輸送系統401a流體連通，反應物輸送系統401a用以輸送處理氣體至分配噴淋頭406。反應物輸送系統401a包含混合容器404，用以混合及∕或調節處理氣體（例如，含鹵素蝕刻劑氣體、或含矽氣體、或含氮氣體）以輸送至噴淋頭406。一或更多混合容器入口閥420可控制處理氣體之導入至混合容器404。
做為一範例，圖4之實施例包含汽化點403，用於汽化待供應至混合容器404之液體反應物。在某些實施例中，汽化點403可為受熱汽化器。由這類的汽化器所產生之飽和反應物蒸氣可能在下游的輸送管路中凝結。不相容氣體暴露至凝結的反應物可能產生小微粒。這些小微粒可能會阻塞管路、妨礙閥操作、污染基板等。解決這些問題之某些方法涉及吹淨及∕或排空輸送管路，以移除殘留的反應物。然而，吹淨輸送管路可能增加處理站循環時間，降低處理站產量。因此，在某些實施例中，汽化點403下游之輸送管路可為伴熱的（heat traced）。在某些範例中，混合容器404亦可為伴熱的。在一非限制性範例中，在汽化點403下游之管路在混合容器404處具有自約100 °C延伸至約150 °C之漸增的溫度曲線。
在某些實施例中，液體前驅物或液體反應物可於液體注入器處進行汽化。例如，液體注入器可注入液體反應物之脈衝至混合容器之上游之載氣氣流中。在一實施例中，藉由使液體從較高壓力快速移動至較低壓力，液體注入器可使反應物汽化。在另一範例中，液體注入器可使該液體霧化為分散的微滴，該分散的微滴隨後在受熱的輸送管路中被汽化。較小的液滴之汽化可能比較大的液滴更快，縮短在液體注入與完全汽化之間之延遲。較快的汽化可減少在汽化點403下游之管路長度。在一情況中，液體注入器可直接安裝至混合容器404。在另一情況中，液體注入器可直接安裝至噴淋頭406。
在某些實施例中，在汽化點403上游之液體流量控制器（LFC）可設置以控制用於汽化及輸送之液體至處理站400之質流。例如，LFC可包含位於LFC下游之熱質流計（MFM）。接著，可調整LFC之柱塞閥，以因應於由比例-積分-微分（PID）控制器（與MFM係電性連通）所提供之反饋控制信號。然而，使用反饋控制可能花費1秒或更久來使液體流量穩定。這可能延長用於注入液體反應物之時間。因此，在某些實施例中，LFC可在反饋控制模式與直接控制模式之間進行動態地切換。在某些實施例中，此可藉由使LFC之感測管、及PID控制器失效而加以執行。
噴淋頭406分配處理氣體朝向基板412。在圖4所示之實施例中，基板412位於噴淋頭406之下方，並且置於基座408上。噴淋頭406可具有任何適當之形狀，並且可具有任何適當數目及配置之埠口，用以分配處理氣體至基板412。
在某些實施例中，基座408可上升或下降，以使基板412暴露至在基板412與噴淋頭406之間之容積。應當了解，在某些實施例中，可藉由適當的電腦控制器450以程式化地調整基座高度。
在另一情況中，調整基座408之高度可容許電漿密度在包含於處理中之電漿活化循環期間進行改變。在處理階段結束時，基座408可在另一基板轉移階段期間下降，以容許基板412從基座408移除。
在某些實施例中，噴淋頭406之位置可相對於基座408而加以調整，以改變在基板412與噴淋頭406之間之容積。此外，應當了解，在本揭露內容之範疇內，基座408及∕或噴淋頭406之垂直位置可藉由任何適當的機構而加以改變。在某些實施例中，基座408可包含旋轉軸，用於旋轉基板412之位向。應當了解，在某些實施例中，這些示例性調整其中一或更多者可藉由一或更多適當的電腦控制器450而程式化地加以執行。
在使用如上所述之電漿之某些實施例中，噴淋頭406及基座408與用來為電漿供電之射頻（RF）電源414及匹配網路416電性連通。在某些實施例中，電漿能量之控制可藉由控制下列之一或更多者：處理站壓力、氣體濃度、RF源功率、RF源頻率、及電漿功率脈衝時序。例如，RF電源414及匹配網路416可操作於任何適當的功率，以形成具有期望組成之自由基物種之電漿。適當功率之範例係包含於上。同樣地，RF電源414可提供任何適當頻率之RF功率。在某些實施例中， RF電源414可配置成彼此獨立地控制高頻及低頻RF電源。示例性低頻RF頻率可包含，但不限於，0 kHz與500 kHz之間之頻率。示例性高頻RF頻率可包含，但不限於，1.8 MHz與2.45 GHz之間之頻率、或大於約13.56 MHz之頻率、或大於27 MHz之頻率、或大於40 MHz之頻率、或大於60 MHz之頻率。應當了解，任何適當的參數都可分離地或連續地加以調控，以提供用於表面反應之電漿能量。可控制及∕或維持電漿條件，俾使由蝕刻劑所產生之電漿優先在特徵部開口或附近進行蝕刻，而不是在特徵部之側壁中或底部。在一非限制性範例中，相對於連續供電之電漿，可使電漿功率間歇性地脈衝化，以減少離子與基板表面之轟擊。
在某些實施例中，電漿可藉由一或更多電漿監控器而受到原位（in-situ）監控。在一情況中，電漿功率可藉由一或更多電壓、電流感測器（例如，VI探針）而加以監控。在另一情況中，電漿密度及∕或處理氣體濃度可藉由一或更多光學放射光譜感測器（OES）而加以量測。在某些實施例中，一或更多電漿參數可基於來自這樣的原位電漿監控器之測量結果而程式化地加以調整。例如，OES感測器可使用在用於提供電漿功率之程式控制之反饋迴路中。應當了解，在某些實施例中，可使用其它監控器以監控電漿及其它處理特性。這樣的監控器可包含，但不限於，紅外線（IR）監控器、音訊監控器、及壓力轉換器。
在某些實施例中，用於控制器450之指令可經由輸入∕輸出控制（IOC）序列指令而提供。在一範例中，用於設定處理階段之條件之指令可包含於處理配方之相對應的配方階段中。在某些情況中，可依序地設置處理配方階段，俾使用於處理階段之所有指令與該處理階段係同時執行。在某些實施例中，用以設定一或更多反應器參數之指令可包含於配方階段中。例如，第一配方階段可包含：用於設定惰性及∕或反應物氣體（例如，如二矽烷之第一前驅物）之流率之指令、用於設定載氣（例如氬）之流率之指令、以及用於第一配方階段之時間延遲指令。後續的第二配方階段可包含：用於調控或停止惰性及∕或反應物氣體之流率之指令、以及用於調控載體或吹淨氣體之流率之指令、以及用於第二配方階段之時間延遲指令。第三配方階段可包含：用於設定蝕刻劑氣體（可為含鹵素氣體，例如三氟化氮）之流率之指令、用於調控載氣之流率之指令、以及用於第三配方階段之時間延遲指令。第四配方階段可包含：用於調控或停止蝕刻劑氣體之流率之指令、用於調控載氣或吹淨氣體之流率之指令、以及用於第四配方階段之時間延遲指令。第五配方階段可包含：用於調控第二反應物氣體（例如氮）之流率之指令、用於調控載氣或吹淨氣體之流率之指令、以及用於第五配方階段之時間延遲指令。應當了解，這些配方階段可在本揭露內容之範疇內以任何適當方式進一步加以再分割及∕或重複。
在某些實施例中，基座408可經由加熱器410而受到溫度控制。此外，在某些實施例中，處理站400之壓力控制可藉由蝶形閥418而提供。如圖4之實施例中所示，蝶形閥418節流下游真空泵（未顯示）所提供之真空。然而，在某些實施例中，處理站400之壓力控制亦可藉由改變一或更多氣體導入至處理站400之流率而加以調整。
如上描述，一或更多處理站可包含於多站處理工具中。 圖5顯示多站處理工具500之實施例之概要圖，具有入站裝載室502及出站裝載室504，入站裝載室502及出站裝載室504其中一或兩者可包含遠端電漿源。在大氣壓力下之機械臂506係用以將晶圓自卡匣（透過盒508而裝載）經由大氣埠510移動至入站裝載室502中。晶圓係藉由機械臂506而放置在入站裝載室502中之基座512上，關閉大氣埠510，且抽空裝載室。在入站裝載室502包含遠端電漿源之情況中，可使晶圓在被導入處理腔室514之前而在裝載室中暴露至遠端電漿處理。此外，晶圓亦可在入站裝載室502中進行加熱，例如，以移除濕氣及吸附的氣體。接著，打開往處理腔室514之腔室傳送埠516，另一機械臂（未顯示）將晶圓放置在反應器中且在第一站（顯示在反應器中）之基座上，以進行處理。雖然圖5中所繪示之實施例包含裝載室，但應當了解，在某些實施例中，晶圓可直接進入處理站中。
在圖5中所示之實施例中，所描繪的處理腔室包含四處理站，編號為1到4。每一站具有受到加熱的基座（顯示於站1之518）、及氣體管線入口。應當了解，在某些實施例中，每一處理站可具有不同或多個目的。例如，在某些實施例中，處理站可在ALD與電漿輔助ALD處理模式之間進行切換。額外或替代地，在某些實施例中，處理腔室514可包含一或更多匹配成對的ALD及電漿輔助ALD處理站。儘管所描繪的處理腔室514包含四站，但應當理解，根據本揭露內容之處理腔室可具有任何適當數目之站。例如，在某些實施例中，處理腔室可具有五或更多站，然而在其它實施例中，處理腔室可具有三或更少站。
圖5描繪晶圓搬運系統590之實施例，用以在處理腔室514中轉移晶圓。在某些實施例中，晶圓搬運系統590可在各種處理站之間及∕或在處理站與裝載室之間轉移晶圓。應當了解，可採用任何適當的晶圓搬運系統。非限制性範例包含晶圓旋轉架及晶圓搬運機械臂。圖5亦描繪系統控制器550之實施例，用以控制處理工具500之處理條件及硬體狀態。系統控制器550可包含一或更多記憶體裝置556、一或更多大容量儲存裝置554、及一或更多處理器552。處理器552可包含CPU或電腦、類比及∕或數位輸入∕輸出連接、步進馬達控制器板等。
在某些實施例中，系統控制器550控制處理工具500之所有活動。系統控制器550執行系統控制軟體558，系統控制軟體558係儲存於大容量儲存裝置554中、載入至記憶體裝置556中、以及在處理器552上執行。或者，可將控制邏輯硬編碼於控制器550中。對於這些目的，可使用特殊應用積體電路、可編程邏輯裝置（例如，場域可編程閘陣列，或FPGA）及類似者。在以下討論中，在使用“軟體＂或“編碼＂之任何情況中，可適當地使用功能上可比較的硬編碼邏輯。系統控制軟體558可包含用以控制以下者之指令：時序、氣體之混合、氣體流率、腔室及∕或站壓力、腔室及∕或站溫度、晶圓溫度、目標功率位準、RF功率位準、基板基座、卡盤及∕或托座位置、及藉由處理工具500而執行之特定處理之其它參數。系統控制軟體558可以任何適當的方式加以配置。例如，可撰寫各種處理工具元件子程序或控制物件，以控制用於實行各種處理工具處理之處理工具元件之操作。系統控制軟體558可以任何適當的電腦可讀程式語言加以編碼。
在某些實施例中，系統控制軟體558可包含輸入∕輸出控制（IOC）序列指令，用以控制上述之各種參數。在某些實施例中，可採用儲存於與系統控制器550相聯繫之大容量儲存裝置554及∕或記憶體裝置556上之其它電腦軟體及∕或程式。用於此目的之程式或程式片段之範例包含基板定位程式、處理氣體控制程式、壓力控制程式、加熱器控制程式、及電漿控制程式。
基板定位程式可包含用於處理工具元件之程式碼，該處理工具元件係用以將基板裝載至基座518上，並且用以控制在基板與處理工具500之其它零件之間之間距。
處理氣體控制程式可包含用以控制氣體組成（例如，如本文所述之含矽氣體、含氮氣體、含鹵素蝕刻劑氣體、及吹淨氣體）及流率之編碼，以及可選地，用以在沉積之前使氣體流動至一或更多處理站中以穩定處理站壓力之編碼。壓力控制程式可包含用以控制處理站內壓力之編碼，其係藉由調節，例如，在處理站之排氣系統中之節流閥、進入處理站之氣體流動、等。
加熱器控制程式可包含用以控制至加熱單元之電流之編碼，加熱單元係用以加熱基板。或者，加熱器控制程式可控制熱轉移氣體（例如，氦）至基板之傳送。
根據本文中之實施例，電漿控制程式可包含用以對施加至一或更多處理站中之處理電極之RF功率位準進行設定之編碼。
根據本文中之實施例，壓力控制程式可包含用以在反應腔室中維持壓力之編碼。
在某些實施例中，可具有與系統控制器550相聯繫之使用者介面。使用者介面可包含顯示螢幕、設備及∕或處理條件之圖形軟體顯示、以及使用者輸入裝置，例如指示裝置、鍵盤、觸控螢幕、麥克風、等。
在某些實施例中，由系統控制器550所調整之參數可能與處理條件有關。非限制性範例包含處理氣體組成及流率、電漿條件（例如，RF偏壓功率位準）、壓力、溫度、等。這些參數可以配方之形式而提供給使用者，配方可利用使用者介面而輸入。
藉由系統控制器550之類比及∕或數位輸入連接，可自各種處理工具感測器而提供用以監控處理之訊號。用以控制處理之訊號可在處理工具500之類比及數位輸出連接上進行輸出。可受監控之處理工具感測器之非限制性範例包含質流控制器、壓力感測器（例如，壓力計）、熱偶等。適當編程之反饋及控制演算法可與來自這些感測器之資料一起用來維持處理條件。
系統控制器550可提供用以實施上述沉積處理之程式指令。程式指令可控制各種處理參數，例如DC功率位準、RF偏壓功率位準、壓力、溫度、等。根據本文中所述之各種實施例，指令可控制參數，以操作膜堆疊之原位沉積。
典型地，系統控制器550將包含一或更多記憶體裝置、以及一或更多用以執行指令之處理器，俾使設備將執行根據所揭露的實施例之方法。機器可讀媒體可耦接至系統控制器550，該機器可讀媒體包含用以根據所揭露的實施例而控制處理操作之指令。
在某些實行例中，系統控制器550為系統的一部分，其可為上述範例之一部分。這樣的系統可包含半導體處理設備，其中包含一處理工具或複數處理工具、一腔室或複數腔室、用以進行處理之一平台或複數平台、及∕或特定的處理元件（晶圓基座、氣體流動系統、等）。這些系統與電子元件整合，電子元件係用以於半導體晶圓或基板之處理之前、期間內、及之後控制它們的操作。電子元件係稱為“控制器＂，該控制器可控制一系統或複數系統之各種元件或子部分。根據處理條件及∕或系統類型，系統控制器550被程式化以控制本文中所揭露的任何處理，包含處理氣體之傳輸、溫度設定（例如，加熱及∕或冷卻）、壓力設定、真空設定、功率設定、射頻（RF）產生器設定、RF匹配電路設定、頻率設定、流率設定、流體傳輸設定、定位及操作設定、晶圓傳遞進入與離開連接至特定系統或與特定系統接合之工具及其它傳遞工具及∕或裝載室。
廣義而言，系統控制器550可定義為具有用以接收指令、發出指令、控制操作、使清洗操作得以進行、使終點測量得以進行、及達成類似功能之各種積體電路、邏輯、記憶體、及∕或軟體之電子元件。積體電路可包含儲存程式指令之韌體形式之晶片、數位信號處理器（DSP）、定義為特殊應用積體電路（ASIC）之晶片、及∕或一或更多微處理器、或執行程式指令（例如，軟體）之微控制器。程式指令可為以各種單獨設定（或程式檔案）之形式通訊至系統控制器550之指令，定義了用以在半導體晶圓上、或對半導體晶圓、或對系統實行特定處理之操作參數。在某些實施例中，操作參數可為由製程工程師所定義以在晶圓之一或更多層、材料、金屬、氧化物、矽、二氧化矽、表面、電路、及∕或晶粒之製造期間內完成一或更多處理步驟之配方之一部分。
在某些實行例中，系統控制器550可為電腦之一部分或耦接至電腦，該電腦與該系統整合、耦接至該系統、以其它方式網路連接至該系統、或其組合。例如，系統控制器550可在“雲端＂中、或使得晶圓處理之遠端控制得以進行之工廠主機電腦系統之全部或一部分。該電腦可使得對系統之遠端控制得以進行以監控製造操作之當前處理、檢驗過去製造操作之歷史記錄、檢驗複數製造操作之趨勢或效能評量、改變當前處理之參數、設置在當前處理之後之處理步驟、或開始新的處理。在某些範例中，遠端電腦（例如伺服器）可透過網路而將處理配方提供至系統，網路可包含區域網路或網際網路。遠端電腦可包含使用者界面，該使用者介面使得參數及∕或設定之輸入或程式化得以進行，該參數及∕或設定接著從遠端電腦被傳遞至該系統。在某些範例中，系統控制器550接收數據形式之指令，指令為待於一或更多操作期間內執行之該等處理步驟其中每一者指定了參數。應當了解，該等參數可針對待執行之處理類型、及系統控制器550與其接合或對其進行控制之工具類型。因此，如上所述，系統控制器550可為分散式的，例如藉由包含以網路連接在一起並朝著共同目標（例如本文中所述之處理及控制）工作之一或更多獨立控制器。用於這樣的目標之分散式控制器之範例將是腔室中之一或更多積體電路，該一或更多積體電路與位於遠端（例如，在平台等級或做為遠端電腦之一部分）之一或更多積體電路通訊相結合，以控制腔室中之處理。
非限制性地，示例性系統可包含電漿蝕刻腔室或模組、沉積腔室或模組、旋轉清洗腔室或模組、金屬鍍腔室或模組、清潔腔室或模組、斜邊蝕刻腔室或模組、物理氣相沉積（PVD）腔室或模組、化學氣相沉積（CVD）腔室或模組、ALD腔室或模組、原子層蝕刻（ALE）腔室或模組、離子植入腔室或模組、軌道腔室或模組、及關於或用於半導體晶圓之加工及∕或製造之任何其它半導體處理系統。
如上所述，取決於欲由工具所執行之處理步驟，系統控制器550可與下列之一或多者通訊：其它工具電路或模組、其它工具元件、叢集工具、其它工具介面、相鄰工具、鄰近工具、位於工廠各處之工具、主電腦、另一控制器、或在半導體製造工廠中將晶圓容器移入及移出工具位置及∕或裝載埠之材料傳送用工具。
用以執行本文中所揭露的方法之適當設備係進一步討論及描述於：2011年4月11日申請、且名稱為“PLASMA ACTIVATED CONFORMAL FILM DEPOSITION＂之美國專利申請案第13/084,399號（現在之美國專利第8,728,956號）；以及2011年4月11日申請、且名稱為“SILICON NITRIDE FILMS AND METHODS＂之美國專利申請案第13/084,305號，其每一者之全部內容係合併於本文中。
本文中所描述之設備∕處理可結合微影圖案化工具或處理而使用，例如，用於半導體元件、顯示器、LED、太陽光電板等之製造或生產。通常，雖然不必然，這樣的工具∕處理將一起使用或執行於共同的製造設施內。膜之微影圖案化通常包含一些或全部下述步驟，每個步驟以幾個可能的工具提供：（1）工作件（亦即基板）上光阻之塗佈，使用旋轉式或噴塗式之工具；（2）光阻之固化，使用加熱板或加熱爐或UV固化工具；（3）以工具（例如晶圓步進機）使光阻暴露於可見光或UV光或x射線光；（4）使光阻顯影以便使用工具（例如溼式清洗台）選擇性地移除光阻及從而使其圖案化；（5）藉由使用乾式或電漿輔助蝕刻工具轉移光阻圖案至下方膜或工作件中；及（6）使用工具（例如RF或微波電漿光阻剝除器）移除光阻。實驗 實驗 1
進行一實驗，以比較由習知ALD處理所沉積之矽氮化物膜、與由所揭露的實施例所沉積之矽氮化物膜之保形性。
在第一試驗中，使基板暴露於50個原子層沉積之循環，其中每一循環涉及使基板暴露至二矽烷、吹淨腔室、使基板暴露至氮並且點燃電漿、及吹淨腔室。在圖6A中顯示具有矽氮化物610沉積於特徵部上之基板600之影像。應當注意，在特徵部頂部之膜比側壁上之膜實質上更厚。
在第二試驗中，根據所揭露的實施例，使基板暴露於50個原子層沉積之循環，其中每一循環涉及使基板暴露至二矽烷、吹淨腔室、使基板暴露至三氟化氮（含鹵素蝕刻劑）、吹淨腔室、使基板暴露至氮並且點燃電漿、及吹淨腔室。使用於兩個試驗之吹淨氣體為氬。在每一循環中，使基板暴露至三氟化氮。在圖6B中顯示具有矽氮化物680沉積於特徵部上之基板600之影像。應當注意，相較於圖6A，在圖6B之特徵部頂部之膜厚度與側壁上之膜厚度實質上更為相近。
對於兩個試驗，測量在特徵部之頂部、在特徵部側壁之頂部、在特徵部側壁之底部、及特徵部之底部之矽氮化物膜之厚度。計算比例，以判定在這些不同部分之間之保形性。當比例較接近100%，則膜為較保形的。結果係顯示在以下之表1中。 表1 有及沒有蝕刻劑（NF3 ）之矽氮化物沉積<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td>   </td><td>   </td><td> 有 蝕刻劑 </td><td> 沒有 蝕刻劑 </td></tr><tr><td> 所沉積的厚度 </td><td> 頂部 (Å) </td><td> 86 </td><td> 98 </td></tr><tr><td> 側壁，頂部 (Å) </td><td> 55 </td><td> 55 </td></tr><tr><td> 側壁，底部 (Å) </td><td> 29 </td><td> 23 </td></tr><tr><td> 底部 (Å) </td><td> 113 </td><td> 36 </td></tr><tr><td> 比例 </td><td> 側壁底部∕頂部之比例 </td><td> 33% </td><td> 23% </td></tr><tr><td> 底部∕頂部之比例 </td><td> 131% </td><td> 37% </td></tr><tr><td> 側壁底部∕側壁頂部之比例 </td><td> 52% </td><td> 29% </td></tr><tr><td> 沉積速率 </td><td> 頂部（Å∕循環） </td><td> 0.43 </td><td> 0.49 </td></tr><tr><td> 側壁，底部（Å∕循環） </td><td> 0.14 </td><td> 0.11 </td></tr></TBODY></TABLE>
如表1所示，相較於沒有蝕刻劑所沉積之膜之比例，具有蝕刻劑所沉積之膜之比例更接近100%。例如，具有蝕刻劑所沉積之膜之側壁底部對側壁頂部之比例為52%，相較於沒有蝕刻劑所沉積之膜之29%。這些結果建議，在使用所揭露的實施例所沉積之膜中之保形性改善，與在原子層沉積處理中納入蝕刻劑暴露有關。結論
儘管上述實施例已為了清楚理解之目的而詳細地加以描述，但顯而易見的，在所附申請專利範圍的範疇中，可實行某些變更及修改。例如，雖然可能以特定順序而顯示或描述各種操作，實行例可包含以其它順序而執行操作之處理，除非有明確地指明。例如，在某些實施例中，本文中所揭露的操作可能以不同於圖式所描繪、或說明書或申請專利範圍所記載之順序加以實施，並且仍可達成良好的效果。此外，在某些實施例中，可能省略各種操作，或可能在所述的操作之外實施一或更多額外的操作。
應當注意，有許多替代的方式來實施本案實施例之處理、系統及設備。因此，本案實施例應被視為是用於說明的而不是限制性的，且本案實施例不應被限制於本文中所提出之細節。
101‧‧‧操作
103‧‧‧操作
105‧‧‧操作
107‧‧‧操作
109‧‧‧操作
111‧‧‧操作
113‧‧‧操作
115‧‧‧操作
200‧‧‧基板
201‧‧‧機制
203‧‧‧機制
205‧‧‧機制
207‧‧‧機制
209‧‧‧機制
211‧‧‧二矽烷分子
217‧‧‧六氟二矽烷
221‧‧‧二矽烷分子
227‧‧‧六氟二矽烷
231‧‧‧二矽烷分子
237‧‧‧矽氮化物
243‧‧‧三氟化氮分子
250‧‧‧氟物種
255‧‧‧氟
260‧‧‧激發的氮物種
265‧‧‧Si-N鍵
300‧‧‧ALD處理
310A, 310B‧‧‧沉積循環
320A, 320B‧‧‧第一前驅物暴露階段
340A, 340B‧‧‧吹淨階段
350A, 350B‧‧‧蝕刻劑階段
355A, 355B‧‧‧吹淨階段
360A, 360B‧‧‧第二反應物與電漿暴露階段
380A, 380B‧‧‧吹淨階段
400‧‧‧原子層沉積處理站
401a‧‧‧反應物輸送系統
402‧‧‧處理腔室體
403‧‧‧汽化點
404‧‧‧混合容器
406‧‧‧分配噴淋頭
408‧‧‧基座
410‧‧‧加熱器
412‧‧‧基板
414‧‧‧射頻電源
416‧‧‧匹配網路
418‧‧‧蝶形閥
420‧‧‧混合容器入口閥
450‧‧‧電腦控制器
500‧‧‧多站處理工具
502‧‧‧入站裝載室
504‧‧‧出站裝載室
506‧‧‧機械臂
508‧‧‧盒
510‧‧‧大氣埠
512‧‧‧基座
514‧‧‧處理腔室
516‧‧‧腔室傳送埠
518‧‧‧基座
550‧‧‧系統控制器
552‧‧‧處理器
554‧‧‧大容量儲存裝置
556‧‧‧記憶體裝置
558‧‧‧系統控制軟體
600‧‧‧基板
610‧‧‧矽氮化物
680‧‧‧矽氮化物
圖1為處理流程圖，描繪根據所揭露的實施例之方法之操作。
圖2A及2B為概要圖，說明根據所揭露的實施例之用以沉積膜之機制之範例。
圖3為時序圖，顯示根據所揭露的實施例之方法中之循環之範例。
圖4為概要圖，說明用以執行所揭露的實施例之示例性處理腔室。
圖5為概要圖，說明用以執行所揭露的實施例之示例性處理工具。
圖6A為沉積在具有特徵部之基板上之矽氮化物膜之影像。
圖6B為在根據所揭露的實施例所執行之一實驗中、沉積在具有特徵部之基板上之矽氮化物膜之影像。
300‧‧‧ALD處理
310A,310B‧‧‧沉積循環
320A,320B‧‧‧第一前驅物暴露階段
340A,340B‧‧‧吹淨階段
350A,350B‧‧‧蝕刻劑階段
355A,355B‧‧‧吹淨階段
360A,360B‧‧‧第二反應物與電漿暴露階段
380A,380B‧‧‧吹淨階段

Claims (20)

  1. 一種在腔室中處理基板之方法，該方法包含： (a) 提供具有一或更多特徵部之一基板，每一特徵部包含一特徵部開口； (b) 在容許一含矽前驅物吸附至該基板之表面上之條件下，使該基板暴露至該含矽前驅物，藉此形成該含矽前驅物之一吸附層； (c) 在使該基板暴露至該含矽前驅物之後，使該基板暴露至一含鹵素蝕刻劑；及 (d) 使該基板暴露至一含氮反應物及點燃電漿，以選擇性地蝕刻在該等特徵部開口或附近之該含矽前驅物之該吸附層，及形成一矽氮化物膜。
  2. 如申請專利範圍第1項之在腔室中處理基板之方法，其中在容許該含鹵素蝕刻劑選擇性吸附至該含矽前驅物之該吸附層上之條件下，使該基板暴露至該含鹵素蝕刻劑。
  3. 如申請專利範圍第1項之在腔室中處理基板之方法，其中該含鹵素蝕刻劑係選自於由三氟化氮、氯、三氟甲烷、四氟化碳、及其組合所組成之群組。
  4. 如申請專利範圍第1項之在腔室中處理基板之方法，其中該含鹵素蝕刻劑包含具有化學式Cn F2n+2 或Cn F2n 之化合物，其中n ＞ 1。
  5. 如申請專利範圍第1-4項其中任一項之在腔室中處理基板之方法，其中在使該基板暴露至該含鹵素蝕刻劑之後，吹淨該腔室。
  6. 如申請專利範圍第5項之在腔室中處理基板之方法，其中藉由使一吹淨氣體流動，以吹淨該腔室，該吹淨氣體係選自於由氬、氦、氮、及氫所組成之群組。
  7. 如申請專利範圍第1-4項其中任一項之在腔室中處理基板之方法，其中該含矽前驅物係選自於由甲矽烷、二矽烷、三矽烷、四矽烷、三矽基胺、胺基矽烷、及鹵代矽烷所組成之群組。
  8. 如申請專利範圍第1-4項其中任一項之在腔室中處理基板之方法，其中該含氮反應物係選自於由氮、氨、聯胺、及胺所組成之群組。
  9. 如申請專利範圍第1-4項其中任一項之在腔室中處理基板之方法，更包含重複步驟 (a) – (d)。
  10. 如申請專利範圍第1-4項其中任一項之在腔室中處理基板之方法，其中在同一腔室中執行步驟 (a) – (d)。
  11. 一種在腔室中處理基板之方法，該方法包含： 藉由執行一或更多循環以沉積一膜，一循環包含： (a) 提供具有一或更多特徵部之一基板，每一特徵部包含一特徵部開口； (b) 在容許一第一前驅物吸附至該基板之表面上之條件下，使該基板暴露至該第一前驅物，藉此形成該第一前驅物之一吸附層； (c) 在使該基板暴露至該第一前驅物之後，使該基板暴露至一含鹵素蝕刻劑；及 (d) 使該基板暴露至一第二反應物及點燃電漿，以選擇性地蝕刻在該等特徵部開口或附近之該第一前驅物之該吸附層，及形成一膜。
  12. 如申請專利範圍第11項之在腔室中處理基板之方法，其中該含鹵素蝕刻劑係選自於由三氟化氮、氯、三氟甲烷、四氟化碳、及其組合所組成之群組。
  13. 如申請專利範圍第11或12項之在腔室中處理基板之方法，其中在步驟 (d) 之前，吹淨該腔室。
  14. 如申請專利範圍第11或12項之在腔室中處理基板之方法，其中該膜係介電膜或金屬膜。
  15. 如申請專利範圍第11或12項之在腔室中處理基板之方法，其中該膜係選自於由矽氮化物、矽碳化物、及矽氧化物所組成之群組。
  16. 如申請專利範圍第11或12項之在腔室中處理基板之方法，其中該第二反應物係氧化劑或還原劑。
  17. 如申請專利範圍第11或12項之在腔室中處理基板之方法，其中每n個循環執行步驟 (d)，其中n係等於或大於1之整數。
  18. 一種處理基板之設備，該設備包含： (a) 至少一處理腔室，該處理腔室包含一基座，用以支托一基板； (b) 至少一出口，用以連接至一真空； (c) 一或更多處理氣體入口，連接至一或更多含矽前驅物源及一或更多含鹵素蝕刻劑； (d) 一射頻（RF）產生器；及 (e) 一控制器，用以控制在該設備中之操作，該控制器包含複數機器可讀指令，該等機器可讀指令係用於： (i) 引入一含矽前驅物至一處理腔室； (ii) 在引入該含矽前驅物之後，引入一含鹵素蝕刻劑至該腔室；及 (iii) 引入一含氮反應物至該腔室及點燃電漿，以形成一矽氮化物膜。
  19. 如申請專利範圍第18項之處理基板之設備，其中該控制器更包含用於在引入該含氮反應物之前、引入一吹淨氣體以吹淨該腔室之機器可讀指令。
  20. 如申請專利範圍第18項之處理基板之設備，其中該含鹵素蝕刻劑係選自於由三氟化氮、氯、三氟甲烷、四氟化碳、及其組合所組成之群組。
TW105109955A 2015-04-03 2016-03-30 藉由原子層沉積及原子層蝕刻的保形膜之沉積 TWI706049B (zh)

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US9502238B2 (en) 2016-11-22
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