TW201921501A - 去除矽氧化膜之方法 - Google Patents

去除矽氧化膜之方法

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Publication number
TW201921501A
TW201921501A TW107125082A TW107125082A TW201921501A TW 201921501 A TW201921501 A TW 201921501A TW 107125082 A TW107125082 A TW 107125082A TW 107125082 A TW107125082 A TW 107125082A TW 201921501 A TW201921501 A TW 201921501A
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TW
Taiwan
Prior art keywords
gas
chamber
silicon oxide
oxide film
film
Prior art date
Application number
TW107125082A
Other languages
English (en)
Inventor
山崎英亮
菊地貴倫
村上誠志
Original Assignee
日商東京威力科創股份有限公司
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Publication date
Application filed by 日商東京威力科創股份有限公司 filed Critical 日商東京威力科創股份有限公司
Publication of TW201921501A publication Critical patent/TW201921501A/zh

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Abstract

提供一種去除矽氧化膜之方法。
在適用一實施形態相關之方法的被加工物中，矽氧化膜係被露出於形成在絕緣膜之開口的底部。此方法係在被加工物表面上共形(CONFORMAL)地形成有保護膜。接著，便藉由來自非活性氣體之電漿的離子所致之濺鍍蝕刻，來蝕刻在矽氧化膜上延伸之保護膜與矽氧化膜的部分區域。接著，便藉由化學性蝕刻來去除矽氧化膜之殘渣。在保護膜之形成中，係重複：使用含碳氣體之前驅體層的形成、利用沖淨所致之多餘前驅體的去除以及利用非活性氣體之電漿所致的前驅體層內之雜質之量的降低。

Description

去除矽氧化膜之方法
本揭露之實施形態係關於一種去除矽氧化膜之方法。
在電子元件之製造中，係在矽區域上之絕緣膜形成有開口，而在該開口形成有連接於矽區域的接觸部。接觸部係使用有例如鈦。在形成接觸部前，便會去除構成矽區域表面之矽氧化膜(自然氧化膜)。此矽氧化膜會被露出在開口底部。
在接觸部形成前所進行之矽氧化膜的去除一般而言，係使用等向性蝕刻。等向性蝕刻已知一種專利文獻1所記載的化學性蝕刻。專利文獻1所記載的化學性蝕刻係使處理氣體中之氟及氯基性氣體與矽氧化膜之氧化矽反應，而從矽氧化膜來形成有改質區域。所形成之改質區域會藉由加熱來被加以去除。
【先前技術文獻】
【專利文獻】
專利文獻1：國際公開第2007/049510號刊物
上述般之等向性蝕刻亦會使絕緣膜從區劃出開口的面沿著橫向被蝕刻。在絕緣膜被蝕刻時，便會在所製作出之電子元件的接觸部間產生電流的溢漏。從而，便會要求要抑制絕緣膜之蝕刻且將被露出在形成於絕緣膜的開口底部之矽氧化膜蝕刻。
一態樣中，便提供一種去除被加工物的矽氧化膜之方法。該被加工物 係具有絕緣膜以及矽氧化膜。矽氧化膜係被露出於形成在絕緣膜的開口底部。一態樣相關之方法係包含：(i)在被加工物之表面上形成含碳之保護膜，保護膜係具有：沿著區劃出開口的絕緣膜之側壁面來延伸的第1區域以及在矽氧化膜上延伸的第2區域之工序；(ii)藉由來自非活性氣體之電漿的離子所致的濺鍍蝕刻來去除保護膜之第2區域與矽氧化膜之工序；以及(iii)藉由化學性蝕刻來去除矽氧化膜之殘渣的工序。形成保護膜之工序係在將被加工物配置於腔室內的狀態下來被加以實行。形成保護膜之工序係實行複數次包含下述各工序的循環：藉由將含碳氣體供給至腔室來在被加工物之表面上形成含碳的前驅體層之工序；將腔室沖淨之工序；藉由在腔室內生成非活性氣體之電漿，來降低被包含在前驅體層的雜質之量的工序；以及將腔室沖淨之工序。
上述方法中，係藉由重複：前驅體層的形成、利用沖淨所致之多餘前驅體的去除以及前驅體層內之雜質量的降低，來形成保護膜。從而，便會在矽氧化膜表面及絕緣膜表面上形成有共形(CONFORMAL)的保護膜。接著，便藉由實行濺鍍蝕刻，來相對於沿著絕緣膜之側壁面延伸的保護膜之第1區域而選擇性地去除在矽氧化膜表面上延伸之保護膜的第2區域及矽氧化膜。之後，便針對矽氧化膜之殘渣來進行等向性的化學性蝕刻。在化學性蝕刻的實行中係藉由保護膜來保護絕緣膜。從而，便可抑制絕緣膜之蝕刻，並蝕刻矽氧化膜。
一實施形態中，含碳氣體係氫氟碳氣體。一範例之含碳氣體可為CH3F氣體。其他實施形態中，含碳氣體係碳化氫氣體。在一實施形態的形成前驅體層的工序中，係可進一步地將氯氣及氫氣中至少一者供給至腔室。根據此實施形態，便可藉由供給氫氣，來形成更加共形的保護膜PF。又，可藉由供給氯氣，來選擇性地形成保護膜。
在一實施形態的降低雜質之量的工序中所使用的非活性氣體係稀有氣體。在一實施形態的去除保護膜之第2區域及矽氧化膜的工序中所使用的非活性氣體係稀有氣體。
一實施形態的去除矽氧化膜之殘渣的工序係包含：藉由對矽氧化膜供 給處理氣體，來從矽氧化膜形成改質區域，改質區域係包含氟矽酸銨之工序；以及藉由加熱具有改質區域之被加工物，來去除改質區域的工序。一實施形態中，處理氣體係可包含HF氣體及NH3氣體。
如上述說明，便可抑制絕緣膜之蝕刻且將被露出在形成於絕緣膜的開口底部之矽氧化膜蝕刻。
1‧‧‧處理系統
PM1、PM2、PM3、PM4‧‧‧程序模組
TM‧‧‧搬送模組
TC‧‧‧腔室
10‧‧‧電漿處理裝置
11‧‧‧腔室本體
11c‧‧‧腔室
12‧‧‧晶座
20‧‧‧排氣機構
31‧‧‧靜電夾具
31a‧‧‧電極
35‧‧‧高頻電源
100‧‧‧處理裝置
112‧‧‧腔室本體
112c‧‧‧腔室
114‧‧‧台座
138‧‧‧排氣裝置
140‧‧‧氣體供給部
160‧‧‧處理裝置
162‧‧‧腔室本體
162c‧‧‧腔室
164‧‧‧台座
166‧‧‧加熱器
170‧‧‧氣體供給部
182‧‧‧排氣裝置
W‧‧‧被加工物
SR‧‧‧矽區域
IF‧‧‧絕緣膜
OP‧‧‧開口
OX‧‧‧矽氧化膜
PF‧‧‧保護膜
R1‧‧‧第1區域
R2‧‧‧第2區域
TR‧‧‧改質區域
圖1係顯示一實施形態相關之去除矽氧化膜的方法之流程圖。
圖2(a)係適用圖1所示之方法前的一範例之被加工物的部分放大剖面圖，圖2(b)、圖2(c)、圖2(d)、圖2(e)以及圖2(f)係圖1所示之方法實行中或實行後的被加工物的部分放大剖面圖。
圖3係顯示可用於圖1所示的方法之實行的處理系統一範例之圖式。
圖4係概略性地顯示可作為圖3所示之處理系統的程序模組來使用之電漿處理裝置之圖式。
圖5係顯示可作為圖3所示之處理系統的程序模組來使用的處理裝置一範例之圖式。
圖6係顯示可作為圖3所示之處理系統的程序模組來使用的處理裝置一範例之圖式。
圖7係顯示在第1評價實驗中所測量的尺寸之圖式。
圖8(a)係顯示在第2評價實驗中所測量的尺寸之圖式，圖8(b)係顯示在比較實驗中所測量的尺寸之圖式。
以下，便參照圖式就各種實施形態來詳細說明。另外，各圖式中係對相同或相當的部分附加相同符號。
圖1係顯示一實施形態相關之去除矽氧化膜的方法之流程圖。圖2(a)係適用圖1所示之方法前的一範例之被加工物的部分放大剖面圖，圖2(b)、圖2(c)、圖2(d)、圖2(e)以及圖2(f)係圖1所示之方法實行中或實行後的被加工物 的部分放大剖面圖。以下，便以圖2(a)所示之被加工物W所適用的情況為範例，來說明圖1所示之方法MT。另外，方法MT係可適用於具有矽氧化膜與絕緣膜，且具有使矽氧化膜露出在形成於絕緣膜之開口底部的構造之任意被加工物。
圖1所示之方法MT係包含工序ST1~工序ST3。方法MT係可進一步地包含工序ST4。方法MT之工序ST1係在被加工物表面上形成有保護膜。如圖2(a)所示，在方法MT適用前，被加工物W係具有矽區域SR以及絕緣膜IF。矽區域SR係由矽所形成。矽區域SR可為例如提供電晶體之源極及汲極的區域。絕緣膜IF係設置於矽區域SR上。絕緣膜IF係由氧化矽之絕緣材料所形成。絕緣膜IF係形成有開口OP。開口OP係例如藉由電漿蝕刻來將遮罩圖案轉印於絕緣膜IF來加以形成。開口OP底部係露出矽氧化膜OX。矽氧化膜OX係藉由例如矽區域SR一部分的氧化(例如自然氧化)來加以形成。
工序ST1係在將被加工物W配置於腔室的狀態下來加以實行。提供此腔室之程序模組係電漿處理裝置。如圖1所示，方法MT之工序ST1係實行複數次循環CY。亦即，工序ST1係實行複數次循環CY。各循環CY係包含工序ST11~工序ST14。
工序ST11係在被加工物W表面上形成有含碳之前驅體層。為了形成前驅體層，工序ST11中係將含碳氣體供給至收納有被加工物W的腔室。藉由使被包含於此含碳氣體的前驅體附著於被加工物W表面或已形成的保護膜上，來形成有前驅體層。
工序ST11所使用的含碳氣體可為如氫氟碳氣體、碳化氫氣體、氟化碳氣體等般的含有碳之任意氣體。工序ST11所使用之含碳氣體可為例如CH3F氣體或C3H6氣體。工序ST11係可進一步地與含碳氣體一同地將載體氣體供給至腔室。載體氣體係非活性氣體，可為例如稀有氣體。工序ST11係可進一步地與含碳氣體一同地將氯氣(Cl2氣體)及氫氣(H2氣體)中至少一者供給至腔室。
接著的工序ST12係實行腔室之沖淨。工序ST12之沖淨係可實行腔室之排氣。工序ST12之沖淨係可將非活性氣體供給至腔室。工序ST12所使用的 非活性氣體係例如稀有氣體。工序ST12所使用之非活性氣體係可為與工序ST11所使用的載體氣體相同之氣體。工序ST12係去除多餘前驅體，亦即，過多地附著於被加工物W或已形成之保護膜上的前驅體。
接著的工序ST13係在腔室內生成非活性氣體之電漿。工序ST13所使用之非活性氣體係例如稀有氣體。工序ST13所使用之非活性氣體係可為與工序ST11所使用的載體氣體，以及工序ST12所使用的非活性氣體相同之氣體。工序ST13係將來自非活性氣體之電漿的離子及/或自由基照射至前驅體層。藉此，便可斷開前驅體層內之碳與雜質(例如，氫及/或氟)之間的鍵結，而去除從碳分離後之雜質。其結果，便可降低前驅體層內之雜質的量。
接著的工序ST14係實行腔室之沖淨。工序ST14之沖淨係可實行腔室之排氣。工序ST14之沖淨係可將非活性氣體供給至腔室。工序ST14所使用的非活性氣體係例如稀有氣體。工序ST14所使用之非活性氣體係可為與工序ST11所使用的載體氣體、工序ST12所使用的非活性氣體以及工序ST13所使用的非活性氣體相同之氣體。亦即，可在工序ST11~工序ST14的實行中連續性地將相同非活性氣體供給至腔室。
在工序ST14實行後，便在工序STJ中判斷是否滿足停止條件。停止條件係判斷在包含工序ST1~工序ST4之循環CY的實行次數達到既定次數時便會被滿足。在工序STJ中判斷停止條件未被滿足時，便再次實行工序ST11。方法MT係實行包含各工序ST11~工序ST14的複數次循環CY。在實行複數次循環CY時，便如圖2(b)所示，在被加工物W表面，亦即在矽氧化膜OX表面上及絕緣膜IF表面上共形地形成有保護膜PF。保護膜PF係包含第1區域R1、第2區域R2以及第3區域R3。第1區域R1係沿著區劃出開口OP的絕緣膜IF之側壁面來加以延伸。第2區域R2係在矽氧化膜OX上延伸。第3區域R3係在絕緣膜IF上面上延伸。
回到圖1，在工序STJ中判斷滿足停止條件時，處理便會前進到工序ST2。工序ST2係藉由來自非活性氣體之電漿的離子所致之濺鍍蝕刻來去除第2區域R2及矽氧化膜OX。工序ST2係藉由濺鍍蝕刻，亦即異向性蝕刻，來相對於第1區域R1而選擇性地蝕刻第2區域R2。工序ST2係使用電漿處理裝 置。此電漿處理裝置可為與工序ST1之實行所使用的程序模組(亦即電漿處理裝置)相同之程序模組，亦可為相異的程序模組。如圖2(c)所示，藉由工序ST2之濺鍍，第3區域R3亦會與第2區域R2及矽氧化膜OX一同地被去除。另外，工序ST2並不會完全地去除矽氧化膜OX，而會殘留有矽氧化膜之殘渣OXR。
如圖1所示，方法MT係接著實行工序ST3。工序ST3係藉由化學性蝕刻來去除矽氧化膜之殘渣OXR。在工序ST3所實行的蝕刻係等向性蝕刻。工序ST3之蝕刻係可使用能夠去除矽氧化膜之殘渣OXR的任意化學性蝕刻。
一實施形態中，工序ST3係包含工序ST31及工序ST32。工序ST31係對矽氧化膜之殘渣OXR供給處理氣體。藉由此處理氣體與矽氧化膜之殘渣OXR反應，便會如圖2(d)所示，形成改質區域TR。改質區域TR係包含氟矽酸銨。此般改質區域TR的形成所使用的處理氣體係包含例如HF氣體及NH3氣體。
接著的工序ST32如圖2(e)所示，係去除改質區域TR。具體而言，工序ST32係加熱具有改質區域TR的被加工物W。藉此，便會使改質區域TR昇華而被排氣。其結果，便會去除矽氧化膜之殘渣OXR。
一實施形態之工序ST3係可實行一次以上包含各工序ST31及工序ST32的循環。工序ST31與工序ST32可使用彼此相異的程序模組來加以實行，亦可使用單一程序模組來加以實行。亦即，工序ST31與工序ST32係可在彼此相異的腔室內來加以實行，或者亦可在單一腔室內來加以實行。一實施形態中，工序S1~工序ST3係可使用單一程序模組來加以實行。亦即，工序ST1~工序ST3係可在將被加工物W配置於單一腔室的狀態下來加以實行。
接著的工序ST4如圖2(f)所示，係去除保護膜PF。保護膜PF係藉由將例如來自包含氫氣及氮氣之處理氣體的電漿之活性基照射至保護膜PF，來被加以去除。工序ST4係可使用與工序ST1~工序ST3之實行所使用的1個以上之程序模組相異的程序模組來加以實行。另外，在工序ST1~工序ST4會使用2個以上的程序模組來實行的情況下，在該2個以上的程序模組間之被加工物W的搬送係僅透過減壓後之環境(例如，下述搬送模組TM的腔室TC)來加 以進行。或者，工序ST1~工序ST4係可使用單一程序模組來加以實行。亦即，工序ST1~工序ST4係可在將被加工物W配置於單一腔室內的狀態下來加以實行。
以上說明之方法MT係在工序ST1中於被加工物W表面上共形地形成有保護膜PF。從而，便可藉由工序ST2之濺鍍蝕刻來在保護膜PF之全區域中殘留下第1區域R1，而去除第2區域R2及矽氧化膜OX。之後，為了去除所殘留的矽氧化膜之殘渣OXR，便在工序ST3中實行化學性蝕刻。在工序ST3的化學性蝕刻之實行中係藉由工序ST2實行後所殘留下的保護膜PF之第1區域R1來保護絕緣膜IF。從而，便可抑制絕緣膜IF的蝕刻，並蝕刻矽氧化膜之殘渣OXR。
一實施形態中，係如上述，在工序ST11中進一步地與含碳氣體一同地將氫氣(H2氣體)及氯氣(Cl2氣體)中至少一者供給至腔室。根據此實施形態，便可藉由供給氫氣(H2氣體)，來形成更加共形的保護膜PF。又，可藉由供給氯氣(Cl2氣體)，來選擇性地形成保護膜。
以下，便就可用於方法MT之實行的處理系統來加以說明。圖3係顯示可用於圖1所示的方法之實行的處理系統一範例之圖式。圖3所示之處理系統1係具備有：台座2a、2b、2c、2d；容器4a、4b、4c、4d；裝載模組LM；對位器AN；裝載互鎖模組LL1、LL2；搬送模組TM；以及程序模組PM1、PM2、PM3、PM4。另外，處理系統1之台座個數、容器個數、裝載互鎖模組個數可為1個以上的任意個數。
台座2a、2b、2c、2d會沿著裝載模組LM的一緣部來加以配列。容器4a、4b、4c、4d會分別配置於台座2a、2b、2c、2d上。容器4a、4b、4c、4d會構成為將被加工物W收納於其內部。各容器4a、4b、4c、4d可為被稱為FOUP(Front-Opening Unified Pod)的容器。
裝載模組LM係於其內部提供腔室LC。腔室LC之壓力會被設定為大氣壓。裝載模組LM係具備搬送裝置TU1。搬送裝置TU1係例如多關節機器人。搬送裝置TU1係構成為會在各容器4a、4b、4c、4d與對位器AN之間、對位器AN與各裝載互鎖模組LL1,LL2之間、各容器4a、4b、4c、4d與各裝載互 鎖模組LL1,LL2之間，透過腔室LC來搬送被加工物W。對位器AN會連接於裝載模組LM。對位器AN會在其內部校正被加工物W之位置。
裝載互鎖模組LL1,LL2係設置於裝載模組LM與搬送模組TM之間。各裝載互鎖模組LL1,LL2會提供預備減壓室。在各裝載互鎖模組LL1,LL2的預備減壓室與腔室LC之間係設置有閘閥。
搬送模組TM會於其內部提供腔室TC。腔室TC係構成為可減壓。在腔室TC與各裝載互鎖模組LL1,LL2之間係設置有閘閥。搬送模組TM係具有搬送裝置TU2。搬送裝置TU2係例如多關節機器人。搬送裝置TU2係構成為會在各裝載互鎖模組LL1,LL2與各程序模組PM1,PM2,PM3,PM4之間、程序模組PM1,PM2,PM3,PM4中任2個程序模組之間，透過腔室TC來搬送被加工物W。
各程序模組PM1,PM2,PM3,PM4係實行專用基板處理的裝置。各程序模組PM1,PM2,PM3,PM4的腔室會透過閘閥來連接於腔室TC。另外，處理系統1之程序模組的個數可為1個以上的任意個數。一範例中，處理系統1的1個程序模組係下述電漿處理裝置，而可使用該電漿處理裝置來實行工序ST1~工序ST4。另一範例中，係使用為處理系統1的1個程序模組之下述電漿處理裝置，來實行工序ST1、工序ST2、工序ST3的工序ST31以及工序ST4，工序ST3之工序ST32係使用該1個程序模組或是相異之程序模組來加以實行。又一範例中，係使用為處理系統1的1個程序模組之下述電漿處理裝置，來實行工序ST1、工序ST2以及工序ST4，工序ST3之工序ST31及工序ST32係使用單一個程序模組或是相異之程序模組來加以實行。工序ST1、工序ST2以及工序ST4亦可使用相異之電漿處理裝置來加以實行，或是使用相同電漿處理裝置來實行工序ST1、工序ST2以及工序ST4中的2個工序。又，程序模組PM1,PM2,PM3,PM4中的1個程序模組可為用以在工序ST4實行後於開口OP內形成接觸部的成膜裝置。
處理系統1係可進一步地具備控制部MC。控制部MC係構成為在方法MT之實行中會控制處理系統1之各部。控制部MC係可為具備有處理器(例如CPU)、記憶體之記憶裝置以及控制訊號之輸出入介面的電腦裝置。記憶裝 置係記憶有控制程式及配方資訊。藉由使處理器依照控制程式及配方資訊來加以動作，來將控制訊號輸出至處理系統1之各部。藉由此般之控制部MC的動作，便可實行方法MT。
以下，便就可作為處理系統1的1個以上的程序模組來使用的電漿處理裝置來加以說明。圖4係概略性地顯示可作為圖3所示之處理系統的程序模組來使用之電漿處理裝置之圖式。圖4所示之電漿處理裝置10係可在工序ST1~ST4中至少1個工序來加以使用。
電漿處理裝置10係具有略圓筒狀之腔室本體11。腔室本體11係由例如鋁所形成。腔室本體11可不施予表面處理。或者，腔室本體11內壁面係可施予OGF(Out Gas Free)陽極氧化處理。腔室本體11係提供其內部空間來作為腔室11c。另外，腔室11c係在腔室本體11之內部空間中為下述噴淋板16下方的空間。
腔室11c內係設置有晶座12。晶座12係藉由其中央下方所設置之圓筒狀支撐構件13來被加以支撐。腔室本體11底部的中央係形成有開口。腔室本體11底部係以關閉該開口的方式來連接有圓筒狀突出部11b。支撐構件13會被突出部11b底部所支撐。
晶座12上係設置有靜電夾具31。被加工物W係被載置於靜電夾具31上面之上。電漿處理裝置10係具備有例如三根升降銷。升降銷係為了將被加工物W配置於靜電夾具31上，及為了讓被加工物W從靜電夾具31朝上方移動而使用之機構。升降銷係可在使該等前端突出於靜電夾具31上面之上的位置與使該等前端從靜電夾具31上面朝下方退離的位置之間移動。
靜電夾具31係在由所謂氧化鋁之介電體所形成之本體的內部具有電極31a。在從直流電源34來將電壓施加至電極31a時，便會在靜電夾具31與被加工物W之間產生靜電引力。藉由所產生之靜電引力，來將被加工物W吸附至靜電夾具31。其結果，被加工物W便會藉由靜電夾具31來被加以保持。
晶座12係具有本體部。晶座12本體部係由例如鋁所形成，其外周係形成有絕緣環。晶座12內部係透過靜電夾具31來設置有用以調整被加工物W之溫度的溫控機構14。溫控機構14係包含形成在晶座12內部之流道。此流 道係供給有控制其溫度之熱交換媒體。此溫控機構14係將被加工物W之溫度調整為適於處理之溫度，例如在10℃~150℃的範圍內之溫度。另外，溫控機構14可包含晶座12內所設置的1個以上的加熱器。1個以上的加熱器可被設置於靜電夾具31內。
腔室本體11上部係設置有噴淋頭15。濆淋頭15係包含噴淋板16。噴淋板16係設置於腔室本體11之頂壁11a下方及靜電夾具31上方。噴淋板16係具有略圓盤形狀。噴淋板16係形成有多數氣體噴出孔17。噴淋板16係可具有例如於鋁製本體之表面設置由氧化釔所構成之熱噴塗膜的構造。噴淋板16與腔室本體11係藉由環狀之絕緣構件16a來加以絕緣。
腔室本體11之頂壁11a中央係設置有氣體導入口18。頂壁11a與噴淋板16之間係設置有氣體擴散空間19。
氣體導入口18係連接有氣體供給機構30之氣體配管30a。來自氣體供給機構30之氣體係從氣體導入口18來被導入至氣體擴散空間19，並在氣體擴散空間19內擴散，而從噴淋板16之氣體噴出孔17來噴出至腔室11c。
氣體供給機構30係具有複數氣體供給源。複數氣體供給源係包含HF氣體、NH3氣體、CXHYFZ氣體、Ar氣體、N2氣體、H2氣體、Cl2氣體的各供給源。另外，CXHYFZ氣體係含碳氣體，例如為CH3F氣體。又，氣體供給機構30係具有用以從該等複數氣體供給源來供給各氣體的複數氣體供給配管。各複數氣體供給配管係設置有開閉閥及流量控制器(例如質流控制器)。從而，便可調整來自各複數氣體供給源的氣體供給或供給停止，以及來自各複數氣體供給源之氣體流量。來自該等複數氣體供給配管的氣體會透過上述氣體配管30a來供給至噴淋頭15。
晶座12會透過匹配器36來連接有高頻電源35。來自高頻電源35之高頻電力會被供給至晶座12。晶座12係具有作為下部電極之機能，噴淋板16係具有作為上部電極之機能。亦即，晶座12與噴淋板16會構成一對平行平板電極。藉由將高頻電力供給至晶座12，便可在腔室11c內生成電容耦合電漿。又，藉由從高頻電源35來將高頻電力供給至晶座12，便可將電漿中之離子吸引至被加工物W。從高頻電源35所輸出之高頻電力的頻率係設定為 在例如0.1~500MHz的範圍內之頻率。從高頻電源35所輸出之高頻電力的頻率係例如13.56MHz。
腔室本體11底部係連接有排氣機構20。排氣機構20係具有第1排氣配管23、第2排氣配管24、第1壓力控制閥25、乾式泵26、第2壓力控制閥27以及渦輪分子泵28。第1排氣配管23係連接於腔室本體11底部所形成的排氣口21。第1壓力控制閥25及乾式泵26係設置於第1排氣配管23上。第2排氣配管24係連接於腔室本體11底部所形成之排氣口22。第2壓力控制閥27及渦輪分子泵28係設置於第2排氣配管24上。在將腔室11c之壓力設定為高壓的成膜處理時，係僅以乾式泵26來進行腔室11c之排氣。在將腔室11c之壓力設定為低壓的電漿處理時，則會使用乾式泵26與渦輪分子泵28兩者。腔室11c之壓力係基於測量該腔室11c之壓力的壓力感應器的檢測值，而藉由控制各第1壓力控制閥25及第2壓力控制閥27的開啟程度來加以調整。
腔室本體11側壁係形成有開口32。被加工物W係在被搬入至腔室11c時，以及從腔室11c被搬出時，會通過開口32。電漿處理裝置10係沿著腔室本體11側壁來設置有用以開閉開口32之閘閥G。另外，被加工物W之搬送係藉由上述搬送裝置TU2來加以進行。
在電漿處理裝置10為了工序ST1之實行而被使用的情況，便會在工序ST11中將前驅體氣體供給至腔室11c，在工序ST12中將非活性氣體供給至腔室11c，在工序ST13中於腔室11c內生成非活性氣體之電漿，在工序ST14中將非活性氣體供給至腔室11c。在工序ST11~ST14的實行中，會藉由排氣機構20來將腔室11c減壓。
在電漿處理裝置10是為了工序ST2之實行而被使用的情況，便會在腔室11c中生成非活性氣體之電漿。在工序ST2之實行中，會藉由排氣機構20來將腔室11c減壓。來自電漿之離子會藉由自偏壓電位或來自高頻電源35之偏壓電力來被吸引至被加工物W。藉此，來實現工序ST2之濺鍍蝕刻。
在電漿處理裝置10是為了工序ST3之實行而被使用的情況，便會在工序ST31中將上述處理氣體供給至腔室11c，在工序ST32中藉由晶座12的1個以上的加熱器來加熱被加工物W。在工序ST3的實行中，會藉由排氣機構20來 將腔室11c減壓。
在電漿處理裝置10是為了工序ST4之實行而被使用的情況，便會在腔室11c內生成包含氫氣及氮氣的處理氣體之電漿。在工序ST4之實行中，會藉由排氣機構20來將腔室11c減壓。
以下，便就可在工序ST31實行中使用的處理裝置來加以說明。圖5係顯示可作為圖3所示之處理系統的程序模組來使用的處理裝置一範例之圖式。圖5所示之處理裝置100係可作為處理系統1的1個程序模組來使用的處理裝置，且可在工序ST31之實行中被加以使用。
處理裝置100係具備腔室本體112。腔室本體112係提供其內部空間來作為腔室112c。在腔室112c內係設置有台座114。台座114上係在略水平的狀態下來載置被加工物W。台座114係構成為會支撐被載置於其上的被加工物W。台座114在俯視觀察下為略圓形。台座114會被固定在腔室本體112底部。台座114係具有溫度調整機構114a。溫度調整機構114a在一範例中係包含台座114內部所形成之流道。腔室本體112外部係設置有熱交換媒體之供給器。台座114內部之流道係從該供給器來供給熱交換媒體(例如冷媒)。供給至台座114內部之流道的熱交換媒體會回到供給器。亦即，會在供給器與台座114內部之流道之間循環有熱交換媒體。藉由將熱交換媒體供給至台座114內部之流道，來調整台座114之溫度。
處理裝置100係進一步地具備有壓力感應器119。壓力感應器119係例如電容壓力計。壓力感應器119係構成為會測量腔室112c之壓力。
腔室本體112在一範例中係包含第1構件116及第2構件118。第1構件116係在腔室112c側邊及下方延伸。第1構件116係包含側壁部116a及底部116b。側壁部116a係具有略圓筒形狀。底部116b會連續於側壁部116a下端。側壁部116a係形成有通道112p。被加工物W在從腔室本體112外部被搬入至腔室112c時，以及從腔室112c被搬出至腔室本體112外部時，係會通過通道112p。為了開放及閉鎖此通道112p，便會沿著側壁部116a來設置有閘閥120。在閘閥120開放通道112p時，腔室112c與搬送模組TM的腔室TC便會互相連通。另一方面，在閘閥120閉鎖通道112p時，便會使腔室112c從搬送模組TM之腔 室TC被加以隔離。
第1構件116會在其上端提供開口。第2構件118會以關閉第1構件116上端之開口的方式來設置於第1構件116上。腔室本體112壁部內係設置有加熱器112h。加熱器112h係例如阻抗加熱器。加熱器112h會加熱腔室本體112。
第2構件118係包含有蓋部122及噴淋頭124。蓋部122會構成第2構件118外側部分。噴淋頭124係設置於蓋部122內側。噴淋頭124係設置於台座114上方。噴淋頭124係包含本體126及噴淋板128。本體126係包含側壁126a及上壁126b。側壁126a為略筒狀，上壁126b會連續於側壁126a上端，而關閉側壁126a之上端。
噴淋板128係設置於本體126下端側及本體126內側。本體126之上壁126b與噴淋板128之間係與噴淋板128平行地設置有板體130。本體126與噴淋板128之間的空間係包含第1空間124a及第2空間124b。第1空間124a係本體126之上壁126b與板體130之間的空間。第2空間124b係板體130與噴淋板128之間的空間。
處理裝置100係進一步地具備有氣體供給部140。噴淋頭124之第1空間124a係連接有氣體供給部140之第1氣體供給配管141。第1空間124a係連接有複數氣體通道132。複數氣體通道132係從板體130延伸至噴淋板128。複數氣體通道132會分別連接於噴淋板128所形成之複數第1氣體噴出孔128a。從第1氣體供給配管141來供給至第1空間124a的氣體係透過複數氣體通道132及複數第1氣體噴出孔128a來朝腔室112c噴出。
噴淋頭124之第2空間124b係連接有氣體供給部140之第2氣體供給配管142。第2空間124b係連接有噴淋板128所形成之複數第2氣體噴出孔128b。從第2氣體供給配管142供給至第2空間124b之氣體係從複數第2氣體噴出孔128b朝腔室112c來噴出。
氣體供給部140除了第1氣體供給配管141及第2氣體供給配管142以外，還包含複數流量控制器144a~144d。複數各流量控制器144a~144d係質流控制器或壓力控制式流量控制器。各流量控制器144a~144d係調整被供給至其輸入端之氣體流量，而從其輸出端來將調整流量後之氣體輸出。
流量控制器144a之輸入端會連接於氣體源146a。氣體源146a係HF(氟化氫)氣體源。流量控制器144a之輸出端係連接於第1氣體供給配管141。流量控制器144b之輸入端會連接於氣體源146b。氣體源146b係NH3(氨)氣體源。流量控制器144b之輸出端係連接於第2氣體供給配管142。流量控制器144c之輸入端會連接於氣體源146c。流量控制器144c之輸出端係連接於第1氣體供給配管141。流量控制器144d之輸入端會連接於氣體源146d。流量控制器144d之輸出端係連接於第2氣體供給配管142。各氣體源146c及氣體源146d係非活性氣體源。例如，氣體源146c係Ar氣體之稀有氣體源，氣體源146d係N2(氮)氣體源。
處理裝置100係進一步地具備有閥136及排氣裝置138。腔室本體112底部係設置有排氣口112e。排氣口112e會連通於腔室112c。排氣裝置138會透過閥136來連接於排氣口112e。閥136係例如自動壓力控制閥。排氣裝置138係包含乾式泵、渦輪分子泵之真空泵。
在將被加工物W收納於腔室112c的狀態下，於將包含HF氣體及NH3氣體的處理氣體供給至腔室112c時，便會使該處理氣體與矽氧化膜之殘渣OXR反應，而從矽氧化膜之殘渣OXR來形成改質區域TR。
以下，便就可在工序ST32之實行中使用的處理裝置來加以說明。圖6係顯示可作為圖3所示之處理系統的程序模組來使用的處理裝置一範例之圖式。圖6所示之處理裝置160係可作為處理系統1的1個程序模組來使用的處理裝置，而可在工序ST32之實行中被加以使用。
處理裝置160係具備腔室本體162。腔室本體162係提供其內部空間來作為腔室162c。腔室162c內係設置有台座164。台座164係構成為會支撐被載置於其上之被加工物W。台座164內係設置有加熱器166。加熱器166係例如阻抗發熱加熱器。
腔室本體162側壁係形成有通道162p。被加工物W在從腔室本體162外部被搬入至腔室162c時，以及從腔室162c被搬出至腔室本體162外部時，係會通過通道162p。為了開放及閉鎖此通道162p，便會沿著腔室本體162之側壁來設置有閘閥168。在閘閥168開放通道162p時，腔室162c與搬送模組TM 的腔室TC便會互相連通。另一方面，在閘閥168閉鎖通道162p時，便會使腔室162c從搬送模組TM之腔室TC被加以隔離。
處理裝置160係進一步地具備氣體供給部170。氣體供給部170係具備流量控制器172。流量控制器172係質流控制器或壓力控制式流量控制器。流量控制器172會調整被供給至其輸入端之氣體流量，而從其輸出端來輸出調整流量後之氣體。流量控制器172之輸出端係連接有氣體源174。氣體源174係非活性氣體源，例如N2(氮)氣體源。流量控制器172之輸出端會透過配管176來連接於腔室162c。處理裝置160係進一步地具備開閉閥180及排氣裝置182。排氣裝置182係包含乾式泵或渦輪分子泵之真空泵。而會透過開閉閥180來連接於腔室162c。
具有上述改質區域TR之被加工物W係從腔室112c而透過腔室TC來被搬送至腔室162c。在腔室162c內，被加工物W會被載置於台座164上。然後，藉由加熱器166來加熱台座164，而使被加工物W被加熱。在被加工物W被加熱時，改質區域TR之氟矽酸銨便會昇華而被排氣。藉此，來蝕刻矽氧化膜之殘渣OXR。
以上，雖已就各種實施形態來加以說明，但並不限於上述實施形態，而可構成各種變形態樣。例如，在方法MT中所使用的電漿處理裝置可為感應耦合型電漿處理裝置，或是為了生成電漿而使用微波之表面波的電漿處理裝置之任意類型的電漿處理裝置。
以下，便就為了方法MT之評價而進行的評價實驗來加以說明。
(第1評價實驗)
第1評價實驗中，係使用電漿處理裝置10來實行工序ST1，以在樣品上形成保護膜PFA。如圖7所示，樣品係具有由氧化矽所形成之絕緣膜IFA，該絕緣膜IFA係形成有開口。開口之寬度係8nm，開口之深度係150nm。以下，便顯示第1評價實驗中之工序ST1條件。
<第1評價實驗中之工序ST1條件>
‧循環CY之實行次數：50次
‧工序ST11： CH3F氣體流量：40sccm
Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
處理時間：5秒
‧工序ST12：Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
處理時間：2秒
‧工序ST13：Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
高頻電源61之頻率：40MHz，150W
處理時間：5秒
‧工序ST12：Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
處理時間：2秒
第1評價實驗中，係測量所形成之保護膜PFA的5處之膜厚T1~T4(參照圖7)。其結果，膜厚T1、T2、T3、T4分別為3.0nm、3.1nm、3.1nm、2.5nm。從而，便確認到藉由工序ST1的實行，便可共形地形成含碳之保護膜。
(第2評價實驗)
第2評價實驗中，係對樣品依序實行工序ST1及工序ST3。如圖8(a)所示，樣品係具有由氧化矽所形成之絕緣膜IFB，該絕緣膜IFB係形成有開口。開口之寬度係9.4nm，開口之深度係192nm。工序ST1係使用電漿處理裝置 10。工序ST31係使用處理裝置100，工序ST32係使用處理裝置160。以下，便顯示第2評價實驗中之工序ST1條件。
<第2評價實驗中之工序ST1條件>
‧循環CY之實行次數：10次
‧工序ST11：C3H6氣體流量：40sccm
Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
處理時間：5秒
‧工序ST12：Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
處理時間：2秒
‧工序ST13：Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
高頻電源61之頻率：40MHz，150W
處理時間：5秒
‧工序ST12：Ar氣體流量：300sccm
靜電夾具31之溫度：60℃
腔室壓力：80mTorr(10.67Pa)
處理時間：2秒
<第2評價實驗中之工序ST3條件>
‧包含工序ST31及工序ST32的循環之實行次數：3次
‧各循環中的工序ST31條件
HF氣體流量：150sccm
NH3氣體流量：90sccm
Ar氣體流量：225sccm
N2氣體流量：225sccm
腔室壓力：450mTorr(60Pa)
台座164之溫度：85℃
處理時間：6秒
‧各循環中的工序ST32條件
工序ST32A：沖淨工序
NH3氣體流量：90sccm
Ar氣體流量：225sccm
N2氣體流量：225sccm
台座164之溫度：85℃
處理時間：5秒
工序ST32B：沖淨工序
腔室：抽真空
氣體流通：無
處理時間：30秒
又，為了比較，便進行比較實驗。比較實驗中，係使用與第2評價實驗所使用之樣品相同的樣品。比較實驗係不對該樣品實行工序ST1而實行工序ST3。比較實驗中之工序ST3條件係與第2評價實驗中之工序ST3條件相同。
第2評價實驗中，係求得工序ST1及工序ST3實行前後的開口之寬度CD1、CD2及CD3(參照圖8(a))的變化量。又，比較實驗中，係求得工序ST3實行前後的開口之寬度CD4、CD5及CD6(參照圖8(b))的變化量。
其結果，CD1之變化量、CD2之變化量、CD3之變化量分別為1nm、0.2nm、1.3nm。另一方面，CD4之變化量、CD5之變化量、CD6之變化量分別為21.9nm、22.8nm、18.6nm。從而，便確認到在不形成保護膜而實行工 序ST3時，絕緣膜IFB會相對於開口而被橫向蝕刻，但在於絕緣膜IFB上形成有保護膜PFB時，則絕緣膜IFB會從工序ST3之蝕刻中被保護。

Claims (9)

  1. 一種方法，係去除被加工物的矽氧化膜之方法，其中該被加工物係具有絕緣膜以及被露出於形成在該絕緣膜的開口之底部中的該矽氧化膜；該方法係包含：在該被加工物之表面上形成含碳之保護膜，該保護膜係具有：沿著區劃出該開口的該絕緣膜之側壁面來延伸的第1區域以及在該矽氧化膜上延伸的第2區域之工序；藉由來自非活性氣體之電漿的離子所致的濺鍍蝕刻來去除該保護膜之該第2區域與該矽氧化膜之工序；以及藉由化學性蝕刻來去除該矽氧化膜之殘渣的工序；形成保護膜之該工序係在將該被加工物配置於腔室內的狀態下來被加以實行；形成保護膜之該工序係實行複數次包含下述各工序的循環：藉由將含碳氣體供給至該腔室來在該被加工物之表面上形成含碳的前驅體層之工序；將該腔室沖淨之工序；藉由在該腔室內生成非活性氣體之電漿，來降低被包含在該前驅體層的雜質之量之工序；以及將該腔室沖淨之工序。
  2. 如申請專利範圍第1項之方法，其中該含碳氣體係氫氟碳氣體。
  3. 如申請專利範圍第2項之方法，其中該含碳氣體係CH 3F氣體。
  4. 如申請專利範圍第1項之方法，其中該含碳氣體係碳化氫氣體。
  5. 如申請專利範圍第1至4項中任一項之方法，其中在形成前驅體層的該工序中，係進一步地將氯氣及氫氣中的至少一者供給至該腔室。
  6. 如申請專利範圍第1至4項中任一項之方法，其中在降低雜質之量的該工序中所使用的該非活性氣體係稀有氣體。
  7. 如申請專利範圍第1至4項中任一項之方法，其中在去除該保護膜之該第2區域及該矽氧化膜之該工序中所使用的該非活性氣體係稀有氣體。
  8. 如申請專利範圍第1至4項中任一項之方法，其中去除該矽氧化膜之 殘渣的該工序係包含：藉由對該矽氧化膜之該殘渣供給處理氣體，來從該矽氧化膜之該殘渣形成改質區域，該改質區域係包含氟矽酸銨的工序；以及藉由加熱具有該改質區域的該被加工物，來去除該改質區域的工序。
  9. 如申請專利範圍第8項之方法，其中該處理氣體係包含HF氣體及NH 3氣體。
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