TWI502652B - 使用製程腔室壁上的矽塗層增強清除殘餘的氟自由基之方法 - Google Patents

使用製程腔室壁上的矽塗層增強清除殘餘的氟自由基之方法 Download PDF

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TWI502652B
TWI502652B TW099112391A TW99112391A TWI502652B TW I502652 B TWI502652 B TW I502652B TW 099112391 A TW099112391 A TW 099112391A TW 99112391 A TW99112391 A TW 99112391A TW I502652 B TWI502652 B TW I502652B
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coating
oxygen
ruthenium
gas
process chamber
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Dongwon Choi
Dong Hyung Lee
Tze Poon
Manoj Vellaikal
Peter Porshnev
Majeed Foad
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Applied Materials Inc
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    • H01J37/32—Gas-filled discharge tubes
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    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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Description

使用製程腔室壁上的矽塗層增強清除殘餘的氟自由基之方法
本發明之實施例係大致上關於半導體基材處理。
互補式金屬氧化半導體(CMOS)技術係廣泛地被應用在積體電路。一種在CMOS元件製造期間通常使用之處理基材的方法係在電漿摻雜製程中涉及例如氟系電漿前驅物的使用。然而，電漿摻雜製程期間所分解之過量的氟自由基會劇烈地腐蝕下方基材上面的下方CMOS結構，造成了顯著的製程整合問題、元件效能劣化、及諸如此類者。
因此，存在一種改良之方法與設備的需求，其中該方法與設備係用以減少在氟系電漿基材製程中之過量氟自由基。
本文係提供用以處理基材之方法與設備。在一些實施例中，一種用於基材處理之設備係包括：一製程腔室，其具有一腔室主體，該腔室主體界定一內部空間；以及一含矽塗層，其設置在該腔室主體之內表面上，其中該含矽塗層之一外表面為至少35%原子數的矽。該製程腔室可以是用於基材處理之任何適當的製程腔室。這可以包括設以形成電漿的製程腔室。所形成的電漿可以是氟系。
在一些實施例中，一種用以在一製程腔室中形成一含矽塗層之方法係包括：提供一包含含矽氣體之第一製程氣體到該製程腔室之內部空間；以及形成一含矽塗層於該製程腔室之一內表面上，其中該含矽塗層之一外表面為至少35%矽。
在一些實施例中，該含矽塗層係由矽構成或實質上由矽構成。在一些實施例中，該含矽塗層可以包含多個交替的矽與氧層以及多個矽層。在一些實施例中，該塗層可以具有設置在一表面上的矽與氧表面，其中該塗層中氧濃度係漸漸地降低，造成了相對的實質矽或富矽的表面。
本發明之實施例係大致上關於用於氟系電漿基材處理之設備與方法。在一些實施例中，提供一具有矽或富矽塗層之製程腔室，以有利地減少腔室中存在的殘餘氟自由基。在一些實施例中，提供用以於製程腔室之內表面上形成塗層之方法。在一些實施例中，在此提供用於電漿摻雜之方法。本發明可以藉由去除製程腔室中殘餘氟自由基而減少基材腐蝕來有利地改善基材處理。
本發明之實施例可以被用在任何適當的製程腔室，例如用於電漿摻雜製程的製程腔室或會在製程腔室中造成過量不期望之氟自由基之任何其他製程的製程腔室。經由非限制的實例，一個這樣的系統為P3i反應器，其可從美國加州聖克拉拉市(Santa Clara)之應用材料公司(Applied Materials,Inc.)獲得，並且其操作方法係揭露於美國專利案號7,166,524，其係讓渡給本案之受讓人且在此以引置方式併入本文作為參考。
根據本發明一些實施例之適於變更且處理基材之一系統的實例係參照第1圖被描述在下文，該第1圖係繪示一環形源電漿離子沈浸佈植反應器100。參照第1圖，環形源電漿離子沈浸佈植反應器100具有一圓柱形製程腔室102，圓柱形製程腔室102係由一圓柱形側壁104與一碟形室頂106來界定。一位在製程腔室之底板的基材支撐件108係支撐一待處理的基材110。一位在碟形室頂106上的氣體散佈板或噴頭112係在其氣體岐管114中自氣體散佈盤116接收製程氣體，其中該氣體散佈盤116的出口可以是來自一或多個個別氣體供應器118之氣體的任一氣體或其混合物。一真空泵120耦接到一泵送環形物122，該泵送環形物122被界定在基材支撐件108與側壁104之間。一處理區域124被界定在基材110與氣體散佈板112之間。
根據本發明，圓柱形側壁之內表面156能夠以一含矽塗層154來塗覆。在一些實施例中，含矽塗層實質上覆蓋腔室主體之內表面156(例如界定內部空間的腔室主體表面)。在一些實施例中，如以下所述，可以在一電漿摻雜製程期間或在這樣的製程之前沉積該含矽塗層154。含矽塗層154可以包括一或多層，並且具有一外表面或部分(例如其面向且暴露於製程腔室之內部)，該外表面或部分為專有的矽、實質上由矽構成(例如約95%或更多原子數的矽)、或為富矽(例如約35%或更多原子數的矽)。提供約35%或更多之矽的塗層(相較於傳統的氧化矽塗層)可以促進增進的氟清除，藉此減少處理期間下方矽元件的腐蝕。
在一些實施例中，如第2A圖所示，含矽塗層154可以是一由矽構成的單層(其實質上由矽構成)或具有一富矽組成。舉例而言，含矽塗層154可以具有約35%或更多之矽組成。
在一些實施例中，如第2B圖所示，含矽塗層154可以是具有一外表面204或部分與一內表面202或部分的單層，其中該外表面204或部分為矽、實質上為矽、或為富矽，如前所述(例如具有約35%或更多之矽組成)，該內表面202或部分包含矽與氧(例如SiOx )。內表面202設置在鄰近圓柱形側壁104之內表面156處(或設置在鄰近形成於圓柱形側壁104之內表面156上的一層處，例如如同下文參照第2C圖所討論者)。塗層中氧濃度朝向外表面204漸漸地降低，使得相對的外表面204具有約35%或更多之矽組成。提供氧化矽(SiOx )之含矽塗層154內表面可促進含矽塗層154對圓柱形側壁104之內表面156之增加的附著性，藉此在處理期間提供少量的微粒形成。含矽層154中矽濃度的變化速率可以是線性的、彎曲的、連續的、非連續的、或其組合。
在一些實施例中，並且如第2C圖所繪示者，含矽塗層154可以是兩或多層，其包含矽與氧之一第一層206(其設置在圓柱形側壁104之內表面156上)與矽之一第二層208(其設置在第一層上)。矽之第二層208可以是任何前述涉及單層含矽塗層154的實施例(例如一階梯狀組成、一純矽組成、一富矽組成、一實質上矽組成、或大致上約35%或更多之矽組成)。在一些實施例中，含矽塗層154可以包含超過兩層(如虛線所繪示之層210)，其中該些交替層包括多個矽與氧層與多個矽層，以及其中至少最外層(例如暴露於處理區域124的層)為任何前述涉及單層含矽塗層154的實施例。
在一些實施例中，包括前述任何實施例，至少最外含矽層可以包含至少一摻質。這樣的摻質可以包括硼(B)、砷(As)、磷(P)、鍺(Ge)、碳(C)、氮(N)、或諸如此類者。將一摻質添加到含矽塗層154之最外表面(或部分)可以進一步促進處理期間氟的清除。在一些實施例中，含矽塗層154中的摻質可以是和處理期間所使用之氟前驅物氣體相同的元素，下文將詳細地討論。
返回第1圖，一對外部重入導管126、128係建立多個供通過處理區域124之電漿流所用的重入環形路徑，該些環形路徑在處理區域124中相交。各導管126、128具 有耦接到製程腔室之相對側的一對末端。各導管126、128為一中空的導電管。各導管126、128具有一D.C.絕緣環132，該絕緣環132係避免一封閉之迴圈導電路徑在導管之兩末端之間形成。各導管126、128的環狀部分係被一環狀磁芯134所圍繞。一環繞該芯134的激化線圈136係經由一阻抗匹配裝置140耦接到一RF功率源產生器138。耦接到個別環狀磁芯134之兩RF功率源產生器138可以具有兩個稍微不同的頻率。自RF功率源138產生器耦接的RF功率在延伸通過個別導管126、128與通過處理區域124之封閉環形路徑中產生電漿離子流。這些離子流震盪於個別RF功率源產生器138的頻率。功率藉由一RF偏壓功率產生器142經由一阻抗匹配電路144或一DC功率源150被施加到基材支撐件108。
電漿形成與後續的基材處理是藉由將一製程氣體或多個製程氣體的混合物經由氣體散佈板112引入圓柱形製程腔室102與從RF功率源產生器138施加足夠的源功率到重入導管126、128以在導管中且在處理區域124中建立環形電漿流來執行。靠近基材表面的電漿通量是由RF偏壓功率產生器142施加的基材偏電壓來決定。電漿速率或通量(每秒接觸每平方公分基材表面的離子數量)是由電漿密度來決動，其中該電漿密度是由RF功率源產生器138所施加之RF功率的位準來控制。基材110處累積的離子劑量(離子數/平方公分)是同時由通量與通量維持的總時間來決定。
若基材支撐件108為一靜電夾盤，則一埋設電極146被提供在基材支撐件之一絕緣板148內，並且該埋設電極146經由阻抗匹配電路144或DC功率源150耦接到RF偏壓功率產生器142。
在運作時，可以從反應器100內的製程氣體產生一電漿，以處理基材110。電漿是在處理區域124中藉由從RF功率源產生器138施加足夠的源功率到重入導管126、128以在導管126、128中且在處理區域124中建立電漿離子流來形成，如前所述。在一些實施例中，可以調整由RF偏壓功率產生器142輸送的基材偏電壓，以控制到基材表面的離子通量。在一些實施例中，沒有偏壓功率被施加。
第3圖係繪示根據本發明一些實施例之一種用以處理基材的方法。第3圖之方法可以參照第1圖之設備來瞭解。方法300大致上開始於步驟302，其中在步驟302時一矽系塗層154可以被形成在製程腔室之內表面156上。矽系塗層154可以是前述任何實施例，並且能夠以各種方式來形成。
舉例而言，如第4圖所示，提供一種用以形成一矽系塗層之方法400，並且方法400開始於步驟402，其中在步驟402時提供一包括含矽氣體之第一製程氣體到製程腔室102。在一些實施例中，含矽氣體可以包含矽烷(SiH4 )。在一些實施例中，第一製程氣體可以進一步包含一惰氣(諸如氬、氦、或諸如此類者)，以增進氣流且促 進電漿引發(ignition)。第一製程氣體能夠以約10sccm至約500sccm之流速被提供到腔室102。
在步驟404，含矽塗層154接著被形成在製程腔室102之內表面156上。含矽塗層可以藉由步驟402提供之含矽氣體在製程腔室102之內表面156上的化學氣相沉積來形成。在一些實施例中，例如，在提供含矽氣體時，製程腔室102可以被維持在約5mTorr至約300mTorr之壓力與約0℃至約65℃之溫度。在一些實施例中，可以提供RF功率，以促進電漿自製程氣體的引發及塗層緻密化。舉例而言，可以提供約200W至約1000W之RF源功率以及選擇性地高達約500W之RF偏壓功率。藉由此製程形成的含矽塗層154可以具有至少約35%矽的組成。第一製程氣體可以被提供且沉積製程可以持續，長達到足以沉積含矽塗層154到約500Å至約10μm之厚度的時段。
在一些實施例中，如第5圖所示，提供一種用以形成矽系塗層之方法500，其中該含矽塗層154包含一第一層(或部分)與一第二層(或部分)，其中第一層包含矽與氧，第二層具有比第一層更高的矽組成。方法500大致上開始於步驟502，其中在步驟502時一包含有含矽氣體與含氧氣體之第一製程氣體被提供到製程腔室102。含矽氣體可以是前述參照第4圖之任何氣體。舉例而言，一適當的含氧氣體是氧(O2 )。在一些實施例中，含矽氣體可以包含矽烷(SiH4 )，並且含氧氣體可以包含氧 (O2 )。第一製程氣體能夠以約10sccm至約500sccm之總流速被提供到腔室102。在含矽氣體和含氧氣體不同的實施例中，含矽氣體與含氧氣體能夠以含矽氣體對含氧氣體之流速比例為約10：1至約1：10來提供。在一些實施例中，含矽氣體與含氧氣體之各者的流速可以為約30sccm至約300sccm。
在步驟504，包含矽與氧之含矽塗層154之第一部分接著被形成在製程腔室102之內表面156上。第一部分可以藉由步驟502提供之含矽氣體在製程腔室102之內表面156上的化學氣相沉積來形成。在一些實施例中，例如，在提供第一製程氣體時，製程腔室102可以被維持在約5mTorr至約300mTorr之壓力與約0℃至約65℃之溫度。在一些實施例中，可以提供RF功率，以促進電漿自製程氣體的引發及Si塗層的塗層緻密化。舉例而言，可以提供約200W至約1000W之RF源功率以及選擇性地高達約500W之RF偏壓功率。藉由此製程形成的含矽塗層154之第一部分可以具有氧化矽(SiOx )的組成。第一製程氣體可以被提供且沉積製程可以持續，長達到足以沉積包含矽與氧之含矽塗層154之第一部分或層到約500Å至約10μm之厚度的時段。
其次，在步驟506，可以減少含氧氣體到製程腔室102之流量(包括藉由終止含氧氣體的流動)。在一些實施例中，可以減少含氧氣體之流量，同時維持第一製程氣體中含矽氣體之流量。在一些實施例中，第一製程氣體之 流動可以被停止，並且一包含含矽氣體(類似於前述討論者)之第二製程氣體可以被提供到製程腔室102。第二製程氣體中含矽氣體可以和第一製程氣體中含矽氣體相同或不同。在一些實施例中，第二製程氣體中含矽氣體和第一製程氣體中含矽氣體相同。
含氧氣體之流量的減少可以是漸漸的(諸如以期望的下降速率)或週期性的，並且可以造成含氧氣體之流動的完全終止。在一些實施例中，可以將含矽氣體對含氧氣體之流速比例從約3：2至約6：1之起初流速比例降低到約10：1至約含純矽氣體之最終流速比例。在一些實施例中，含矽氣體對含氧氣體之起初流速比例(以實際的sccm)可以為約300：200至約300：50，並且最終流速比例可以為約300：30至約300：0。
其次，在步驟508，一矽系塗層(例如外表面204或第二層208)可以藉由例如於和前述討論者相同的溫度和壓力條件下的化學氣相沉積被形成在矽與氧系塗層(例如內表面202或第一層206)之上。含氧氣體之流速的降低可促進含矽塗層154之矽含量的增加，從而沉積組成為至少約35%矽之含矽塗層154之一第二部分(或層)。第二製程氣體可以被提供且沉積製程可以持續，長達到足以沉積包含矽之含矽塗層154之第二部分或層到約500Å至約10μm之厚度的時段。
在一些實施例中，包含第一部分與較高濃度矽第二部分的矽與氧係共同形成含矽塗層154(例如參見第2B 圖)。在一些實施例中，包含第一層與較高濃度矽第二層的矽與氧係共同形成含矽塗層154(例如參見第2C圖)。在一些實施例中，前述製程可以依需求被重複，以形成任何期望之交替層的數量以形成含矽塗層154。舉例而言，含矽塗層154可以包括一或多個中間層(或部分)，其設置在第一層(或部分)與第二層(或部分)之間。在一些實施例中，一包含矽之第三層可以被設置在包含矽與氧之第一層上(例如介於第一層與第二層之間)，並且一包含矽與氧之第四層可以被設置在第三層上(例如介於第三層與第二層之間)。這樣的含矽塗層154將包括一包含矽與氧之第一層(其設置在製程腔室之內表面上)、一包含矽之第三層(其設置在第一層上)、一包含矽與氧之第四層(其設置在第三層上)、以及一包含至少35%矽之第二層(其設置在第四層上)。前述該些層(即第一、第二、第三與第四層)能夠以類似在此討論之層的方式來形成，並且可以具有類似在此討論之層的任何組成。
在一些實施例中，諸如任何前述實施例，第一或第二製程氣體也可以包括一含摻質氣體以用於提供諸如硼(B)、砷(As)、磷(P)、鍺(Ge)、碳(C)、氮(N)等之摻質。含摻質氣體可以和含矽氣體相同或不同。適當的含摻質氣體的實例係包括BF3 、B2 H6 、AsH3 、PH3 、PF3 、GeH4 、CF4 、或諸如此類者。在含矽氣體和含摻質氣體隔開的實施例中，含矽氣體與含摻質氣體能夠以含矽氣體對含摻質氣體之流速比例為約10：1至約1：10(或在一些實施例 中，以sccm，約300：30sccm至約30：300sccm)來提供。在一些實施例中，藉由此方法所形成的含矽塗層154(或至少其一外部或第二層)可以具有至少約1%之一或多種前述摻質的組成。
在一些實施例中，諸如任何前述實施例，含矽塗層154可以經由一電漿增強CVD製程來形成。在任何前述的化學氣相沉積製程中，可以形成一電漿，同時將製程腔室壓力維持在約10mTorr至約100mTorr。在一些實施例中，藉由以約11MHz至約14MHz之頻率來提供約100W至約1500W之源RF功率，電漿係被形成。
除了前述說明，在沉積含矽塗層154到期望的厚度時，可以調控額外的製程參數。舉例而言，在一些實施例中，化學氣相沉積製程所執行的時間量可以被設定於一預定的處理期間，或被設定在沉積了期望的含矽塗層154(或其部分或層)厚度之後。
返回第3圖，其次，在步驟304，一含氟氣體被提供到製程腔室102作為一用於處理基材110之電漿前驅物。在一些實施例中，含氟氣體可以包含諸如諸如硼、砷、磷、鍺、碳、氮等之摻質。舉例而言，在一些實施例中，含氟氣體可以包含三氟化硼(BF3 )、三氟化磷(PF3 )、五氟化磷(PF5 )、三氟化砷(AsF3 )、五氟化砷(AsF5 )等。含氟氣體能夠以約5sccm至約350sccm之流速被提供到製程腔室102。
其次，在步驟306，一電漿自含氟氣體被形成，以促 進基材110的處理。在一些實施例中，形成該電漿，同時將製程腔室102之壓力維持在約5mTorr至約100mTorr。在一些實施例中，藉由以約40kHz至約14MHz之頻率來提供約100W至約3000W之RF源功率，電漿係被形成。一旦完成了基材110的電漿摻雜，方法300大致上停止，並且基材110可以依需求進一步地被處理。
因此，本文已經提供了用於氟系電漿基材處理之設備與方法。在一些實施例中，提供一具有矽或富矽塗層之製程腔室，以有利地減少腔室中存在的殘餘氟自由基。本發明可以藉由去除製程腔室中殘餘氟自由基而減少基材腐蝕來有利地改善基材處理。
儘管前述說明係導向本發明之實施例，可以在不脫離本發明之基本範疇下設想出本發明之其他與進一步實施例。
100‧‧‧反應器
102‧‧‧圓柱形製程腔室
104‧‧‧圓柱形側壁
106‧‧‧碟形室頂
108‧‧‧基材支撐件
110‧‧‧基材
112‧‧‧氣體散佈板/噴頭
114‧‧‧氣體岐管
116‧‧‧氣體散佈盤
118‧‧‧氣體供應器
120‧‧‧真空泵
122‧‧‧泵送環形物
124‧‧‧處理區域
126、128‧‧‧外部重入導管
130‧‧‧末端
132‧‧‧DC絕緣環
134‧‧‧環狀磁芯
136‧‧‧激化線圈
138‧‧‧RF功率源產生器
140‧‧‧阻抗匹配裝置
142‧‧‧偏壓功率產生器
144‧‧‧阻抗匹配電路
146‧‧‧埋設電極
148‧‧‧絕緣板
150‧‧‧DC功率源
154‧‧‧含矽塗層
156‧‧‧內表面
202‧‧‧內表面
204‧‧‧外表面
206‧‧‧第一層
208‧‧‧第二層
210‧‧‧層
300‧‧‧方法
300-306‧‧‧步驟
400‧‧‧方法
402-404‧‧‧步驟
500‧‧‧方法
502-508‧‧‧步驟
可藉由參考本發明之實施例來詳細瞭解本發明之說明，其簡短地在前面概述過，其中該些實施例在附圖中示出。但是應注意的是，附圖僅示出本發明之典型實施例，因此不應視為對其範圍之限制，因為本發明可允許其他等效實施例。
第1圖係繪示根據本發明一些實施例之用以處理半導體基材之設備。
第2A-C圖係繪示根據本發明一些實施例之設置在製程腔室之內表面上之一含矽塗層的實施例。
第3圖係繪示根據本發明一些實施例之用以處理基材之方法。
第4圖係繪示根據本發明一些實施例之用以在製程腔室之內表面上形成一含矽塗層之方法。
第5圖係繪示根據本發明一些實施例之用以在製程腔室之內表面上形成一含矽塗層之方法。
為促進了解，在可能時使用相同的元件符號來表示該等圖式共有的相同元件。圖式並未依比例繪製，並且為了清晰起見係被簡化。應瞭解，一實施例的元件與特徵結構可有利地併入其他實施例而不需特別詳述。
100‧‧‧反應器
102‧‧‧圓柱形製程腔室
104‧‧‧圓柱形側壁
106‧‧‧碟形室頂
108‧‧‧基材支撐件
110‧‧‧基材
112‧‧‧噴頭
114‧‧‧氣體岐管
116‧‧‧氣體散佈盤
118‧‧‧氣體供應器
120‧‧‧真空泵
122‧‧‧泵送環形物
124‧‧‧處理區域
126、128‧‧‧外部重入導管
130‧‧‧末端
132‧‧‧DC絕緣環
134‧‧‧環狀磁芯
136‧‧‧激化線圈
138‧‧‧RF功率源產生器
140‧‧‧阻抗匹配裝置
142‧‧‧偏壓功率產生器
144‧‧‧阻抗匹配電路
146‧‧‧埋設電極
148‧‧‧絕緣板
150‧‧‧DC功率源
154‧‧‧含矽塗層
156‧‧‧內表面

Claims (17)

  1. 一種用於基材處理之設備，包含：一製程腔室，其具有一腔室主體，該腔室主體界定一內部空間；以及一含矽與氧之單一塗層，其設置在該腔室主體之一內表面上，其中該塗層具有一靠近該腔室主體之該內表面之內表面與一外表面，該塗層之該外表面為至少35%原子數的矽，及其中氧濃度從該塗層之該內表面降低至該塗層之該外表面。
  2. 如申請專利範圍第1項所述之設備，其中該設備係用於該內部空間中的電漿處理。
  3. 如申請專利範圍第2項所述之設備，其中電漿係沿著一環形路徑流動，並且其中該內部空間形成該環形路徑之一部分。
  4. 如申請專利範圍第1項所述之設備，其中該塗層係實質上覆蓋界定該內部空間之該腔室主體之表面。
  5. 如申請專利範圍第1項所述之設備，其中該塗層之該外表面為至少95%原子數的矽。
  6. 如申請專利範圍第1項所述之設備，其中該塗層之該外表面為實質上完全原子數的矽。
  7. 如申請專利範圍第1項所述之設備，其中靠近該塗層之該外表面處的氧濃度係實質上為零。
  8. 如申請專利範圍第1項所述之設備，其中該塗層更包含硼、砷、鍺、碳、氮、或磷之至少一者。
  9. 一種用以在一製程腔室中形成一塗層之方法，包含：提供一包含含矽氣體與含氧氣體之第一製程氣體到該製程腔室之一內部空間；以及至少部分地自該第一製程氣體形成一含矽與氧之單一塗層於該製程腔室之一內表面上，其中該塗層具有一靠近該腔室主體之該內表面之內表面與一外表面，該塗層之該外表面為至少35%原子數的矽，及其中氧濃度從該塗層之該內表面降低至該塗層之該外表面。
  10. 如申請專利範圍第9項所述之方法，其中該第一製程氣體包含矽烷(SiH4 )。
  11. 如申請專利範圍第9項所述之方法，其中該第一製程氣體更包含硼、砷、鍺、碳、氮、或磷之至少一者。
  12. 如申請專利範圍第9項所述之方法，其中該塗層之該外表面為至少95%原子數的矽。
  13. 如申請專利範圍第9項所述之方法，其中該含氧氣體為氧。
  14. 如申請專利範圍第9項所述之方法，其中該塗層之該外表面為實質上完全原子數的矽。
  15. 如申請專利範圍第9項所述之方法，其中在該第二層之該外表面處的氧濃度係實質上為零。
  16. 如申請專利範圍第9項所述之方法，更包含：將一基材放置在該製程腔室中；提供一含氟氣體電漿前驅物到該製程腔室；自該含氟氣體在該製程腔室中形成一電漿；以及以電漿處理該基材。
  17. 如申請專利範圍第16項所述之方法，其中該含氟氣體更包含硼、砷、鍺、碳、氮、或磷之至少一者。
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