TWI794238B - 於單一加工腔室中自半導體膜移除氧化物及碳之裝置及方法 - Google Patents
於單一加工腔室中自半導體膜移除氧化物及碳之裝置及方法 Download PDFInfo
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Abstract
本發明揭示一種用來自單一製程腔室內之半導體基板移除碳基污染物及氧基污染物兩者的系統及方法。本發明可包括利用遠端電漿單元及多種氣體源來於單一製程腔室內進行製程。
Description
本發明大體上係關於用於製造電子器件之裝置及方法。更特定言之，本發明係關於移除在加工腔室中形成之半導體膜內的氧化物及碳。
在製造半導體器件之前，需要晶圓或基板的潔淨表面。基板上的污染物會不利地影響所形成半導體器件的機器及電性質。希望在將特定膜沉積於基板上之前移除此等污染物。
存在於矽或矽鍺基板上之污染物可包括碳基污染物，諸如含碳污染物及烴污染物。其他污染物可包括氧基污染物，諸如，比方說，天然氧化物。在可進行磊晶製程之前移除此等污染物可係必要的。
先前的污染物移除方法著重在移除碳基或氧基污染物中之一者，而非兩者。此部分可歸因於先前方法的設備限制。因此，需要移除碳基及氧基污染物兩者的系統及方法。
本發明之目的為提供提供一種用來自單一製程腔室內之半導體
基板移除碳基污染物及氧基污染物兩者的系統及方法。
100:系統
110:反應腔室
120:基座
130:噴淋頭
140:遠端電漿單元
145:輸送路徑
150:基板
160:第一氣體源
170:第二氣體源
180:第三氣體源
190:第四氣體源
200:系統
210:反應腔室
220:基座
230:噴淋頭
240:第一遠端電漿單元
245:第二遠端電漿單元
246:輸送路徑
247:輸送路徑
248:第一閘閥
249:第二閘閥
250:基板
260:第一氣體源
270:第二氣體源
280:第三氣體源
290:第四氣體源
300:步驟
310:步驟
320:步驟
400:步驟
410:步驟
420:步驟
500:步驟
510:步驟
520:步驟
600:重複循環
本文所揭示的本發明之此等及其他特徵、態樣及優點在下文參考某些具體例之圖式來描述，該等具體例意欲說明且不限制本發明。
圖1係根據本發明之至少一個具體例之系統的橫截面圖式。
圖2係根據本發明之至少一個具體例之系統的橫截面圖式。
圖3A、3B及3C為根據本發明之至少一個具體例之方法的流程圖。
圖4為根據本發明之至少一個具體例之步驟的流程圖。
圖5為根據本發明之至少一個具體例之步驟的流程圖。
圖6為根據本發明之至少一個具體例之步驟的流程圖。
儘管在下文中揭示特定具體例及實施例，但彼等熟悉本技藝者應理解，本發明延伸超出本發明所具體揭示之具體例及/或用途及其明顯修改及等效物。因此，希望所揭示之本發明之範疇不應受下文所描述之具體揭示之具體例限制。
本發明之具體例係關於一種包括具有移除碳基污染物及氧基污染物兩者之能力之單一製程腔室的系統。該等具體例具有優於先前方法之若干優點，包括：(1)併入至少一個具有產生氫自由基及氟自由基兩者之能力的遠端電漿單元(RPU)；及(2)製程腔室與氫自由基及氟自由基兩者之相容性。
可使用本發明之具體例來清潔由例如以下材料中之至少一者製成的半導體基板：矽；矽鍺；或鍺。在一個具體例中，矽鍺中之鍺的百分比可自10%變化至90%。此外，可使用本發明之具體例來蝕刻碳層，諸如先進圖案化膜(APF)；光阻劑；或包括CHFx、SiC、或SiOC之其他碳污染物。此外，可使用本發明之具體例來清潔諸如氧化矽、氮化矽、氧氮化矽、氟化氧化矽、碳氧化矽、及碳氧氮化矽之介電材料之表面。此外，可將本發明之具體例應用至圖案化晶圓表面。
圖1說明根據本發明之至少一個具體例之系統100。系統100可包括反應腔室110、基座120、噴淋頭130、遠端電漿單元140、及在遠端電漿單元140與反應腔室110之間的輸送路徑145。基板150置於基座120上用來加工。
反應腔室110界定於其中加工基板150的空間。反應腔室110、基座120、噴淋頭130、及輸送路徑145可經塗布材料或塊狀陶瓷材料以容許與不同自由基的相容性。用來塗布的材料可包括下列中之至少一者：陽極氧化氧化鋁(Al2O3)；原子層沉積(ALD)形成之氧化鋁；電漿噴霧Al2O3；具有天然氧化鋁、氧化釔(Y2O3)之裸鋁部件；經氧化釔穩定之氧化鋯(YSZ)；氧化鋯(ZrO2)；氧化鑭鋯(LZO)；釔鋁石榴石(YAG)；氧氟化釔(YOF)；以上材料之組合；或摻雜其他玻璃相材料之以上基板。在一些情況中，塗布材料可利用兩層製成。例如，第一層可利用陽極氧化Al2O3塗布及第二層可利用ALD形成之Al2O3塗布。塗料可係非晶相、結晶相、或混合的。塊狀陶瓷材料可包括：氧化鋁(Al2O3)；氧化鋯(ZrO2)；氧化釔(Y2O3)；或經氧化釔穩定之氧化鋯(YSZ)。
系統100亦可包括第一氣體源160、第二氣體源170、第三氣體源180、及第四氣體源190，其等皆可將氣體提供至遠端電漿單元140。遠端電漿單元140可包括，例如，來自MKS Instruments之Paragon H*遠端電漿單元。第三氣體源180亦可經組構以將氣體直接提供至反應腔室110，而不經過遠端電漿單元140。第一氣體源160可包括，例如，產生氟自由基之前驅體氣體的來源，諸如NF3、CF4、C2F6、C4F6、C4F8、COF2、SF6、或WF6。第二氣體源170可包括，例如，產生氫自由基之氣體的來源，諸如H2、NH3、或H2O。第二氣體源170可包 括，例如，產生氧自由基之氣體，諸如氧或臭氧。第三氣體源180可為NH3之來源。第四氣體源190可為，例如，惰性氣體之來源，諸如氬、氦、氮、或氖。
遠端電漿單元140產生提供自氣體源之自由基。所產生之自由基接著通過噴淋頭130進入反應室110，及隨後於基板150上流動。遠端電漿源可包括：藉由諸如400kHz、2MHz、60MHz之不同RF頻率驅動之環狀型式ICP源或線圈型式ICP源及2.56GHz微波源。
圖2說明根據本發明之至少一個具體例之系統200。系統200可包括反應腔室210、基座220、噴淋頭230、專用來利用F*移除氧化物之第一遠端電漿單元240、專用來利用H*移除碳之第二遠端電漿單元245、在第一遠端電漿單元下方之輸送路徑246、及在第二遠端電漿單元下方之輸送路徑247。基板250置於基座220上用來加工。系統200亦可包括第一閘閥248及第二閘閥249。
反應腔室210界定於其中加工基板250的空間。反應腔室210、基座220、及噴淋頭230可經塗布材料或塊狀陶瓷材料以容許與不同自由基的相容性，諸如：陽極氧化氧化鋁(Al2O3)；原子層沉積(ALD)形成之氧化鋁；電漿噴霧Al2O3；具有天然氧化鋁之裸鋁部件；氧化釔(Y2O3)；經氧化釔穩定之氧化鋯(YSZ)；氧化鋯(ZrO2)；氧化鑭鋯(LZO)；釔鋁石榴石(YAG)；氧氟化釔(YOF)；以上材料之組合；或摻雜其他玻璃相材料之以上基板。在一些情況中，塗布材料可利用兩層製成。例如，第一層可利用陽極氧化Al2O3塗布及第二層可利用ALD形成之Al2O3塗布。塗料可係非晶相、結晶相、或混合的。塊狀陶瓷材料可包括：氧化鋁(Al2O3)；氧化鋯(ZrO2)；氧化釔(Y2O3)；或經氧化釔穩定之氧化鋯(YSZ)。除以上用於不同自由基之塗料及塊狀材料外，用於第二遠端電漿單元下方之輸送路徑247的材料亦可包含塊狀石英材料。
系統200亦可包括第一氣體源260、第二氣體源270、第三氣體源280、及第四氣體源290，其等皆可將氣體提供至第一遠端電漿單元240及第二遠 端電漿單元245。第一遠端電漿單元240及第二遠端電漿單元245可包括，例如，藉由諸如400kHz、2MHz、60MHz之不同RF頻率驅動之環狀型式ICP源或線圈型式ICP源及2.56GHz微波源。第三氣體源280亦可經組構以將氣體直接提供至反應室210，而不經過第一遠端電漿單元240或第二遠端電漿單元245。第一氣體源260可包括，例如，產生氟自由基之前驅體氣體的來源，諸如NF3、CF4、C2F6、C4F6、C4F8、COF2、SF6、或WF6。第二氣體源270可包括，例如，產生氫自由基之氣體的來源，諸如H2、NH3、或H2O。第二氣體源270可包括，例如，產生氧自由基之氣體，諸如氧或臭氧。第三氣體源280可為NH3之來源。第四氣體源290可為，例如，惰性氣體之來源，諸如氬、氦、氮、或氖。
第一遠端電漿單元240(其可專用於F*自由基)及第二遠端電漿單元245(其可專用於H*自由基)產生提供自氣體源之自由基。所產生之自由基接著通過噴淋頭230進入反應腔室210，及隨後於基板250上流動。為防止由一個遠端電漿單元所產生之自由基往回串流至第二遠端電漿中，可將閘閥248及249設置於RPU之出口處。
圖3A說明根據本發明之至少一個具體例之方法。該方法包括氧化物轉化步驟300、氧化物昇華步驟400、及碳移除步驟500。可視需要重複任何此等步驟或此等步驟之任何組合。可通過重複循環600重複整個方法。
圖3B說明根據本發明之至少一個具體例之方法。該方法包括碳移除步驟500、氧化物轉化步驟300、及氧化物昇華步驟400。可視需要重複任何此等步驟或此等步驟之任何組合。可通過重複循環600重複整個方法。圖3B之方法與圖3A之方法的不同處在於碳移除步驟500在氧化物轉化步驟300之前。
圖3C說明根據本發明之至少一個具體例之方法。該方法包括碳移除步驟500、氧化物轉化步驟300、及氧化物昇華步驟400、及碳移除步驟500。可視需要重複任何此等步驟或此等步驟之任何組合。可通過重複循環600重複整 個方法。圖3C之方法與圖3B之方法的不同處在於在氧化物昇華步驟400之後的額外碳移除步驟500。
根據本發明之至少一個具體例，將氧化物轉化步驟300說明於圖4。氧化物轉化步驟300可包括使氣態前驅體流入至遠端電漿單元中之步驟310及使所產生之自由基及額外前驅體於基板上流動之步驟320。根據本發明之至少一個具體例，步驟310可包括使氬、氫、及NF3流入至遠端電漿單元中。氬之流量可介於0.01與20slm之間、介於0.1與10slm之間、或介於1與8slm之間。氫之流量可介於10sccm與1500slm之間、介於25與1200slm之間、或介於50sccm與1000slm之間。NF3之流量可在電漿於遠端電漿單元中打開時發生介於0.1與120秒之間、介於1與100秒之間、或介於5與80秒之間之特定量的時間。步驟310可包括將反應腔室210加熱至介於5至120℃、介於5至80℃、或介於5至60℃之間的溫度。
由於步驟310之結果，於遠端電漿單元中產生氟自由基之氣體。氟自由基離開遠端電漿單元且可與步驟320中之視情況選用之額外前驅體氣體於安置於反應腔室中之基板上組合。視情況選用之額外前驅體氣體可包括以介於10sccm與1500slm、介於25與1200slm、或介於50sccm與1000slm之間之速率流動的氨。步驟320可包括將反應腔室210加熱至介於5至120℃、介於5至80℃、或介於5至60℃之間的溫度。氧化物轉化步驟300可與具有氧化物之矽鍺基板上之氧化物產生如下之化學反應：NH4F(g)+SiGeOx(s) → (NH4)2SiF6(s)+(NH4)2GeF6(s)+H2O(g)
由於氧化物轉化步驟300之結果，氧化物可於基板上轉變為固態六氟矽酸銨化合物及固態六氟鍺酸銨化合物。
根據本發明之至少一個具體例，將氧化物昇華步驟400說明於圖5。氧化物昇華步驟400包括第一加熱步驟410、或第二加熱步驟420、或兩者。第一加熱步驟410可包括將基板加熱至大於125℃、大於100℃、或大於90℃之溫度。第一步驟410之結果可係固態六氟矽酸銨化合物根據以下反應昇華：(NH4)2SiF6(s) → NH3(g)+HF(g)+SiF4(g)氣態產物隨後可自反應腔室移除。
第二加熱步驟420可包括將基板加熱至高於第一加熱步驟410之溫度。該溫度可係大於275℃、大於250℃、或大於225℃。為達到高操作溫度，可設計高溫噴淋頭以加熱至250℃-300℃而不加熱反應腔室。第二步驟420之結果可係固態六氟鍺酸銨化合物根據以下反應昇華：(NH4)2GeF6(s) → NH3(g)+HF(g)+GeF4(g)氣態產物隨後可自反應腔室移除。
根據本發明之至少一個具體例，將碳移除步驟500說明於圖6。碳移除步驟500包括使氫前驅體及其他氣態前驅體流入至遠端電漿單元中之步驟510及使所產生之自由基及視情況選用之額外前驅體於基板上流動之步驟520。第一加熱步驟510可包括使氬、氫、及氨流入至遠端電漿單元中。該等氣體可流動介於0.1與180秒之間、介於1與120秒之間、或介於10與90秒之間的持續時間。結果，於遠端電漿單元中產生氫自由基。
步驟520使所產生之氫自由基與基板中之碳基污染物反應。此步驟可在介於25℃與500℃之間、介於75℃與400℃之間、或介於150℃與300℃之間的溫度下發生。較高溫的噴淋頭可容許加熱基板並導致有效移除碳。步驟520之結果可係根據以下反應移除碳：C(s)+H*(g) → CxHy(g)其他反應可包括碳與氧自由基。氣態產物隨後可自反應腔室移除。
所展示且描述之特定實施方案係對本發明及其最佳模式之說明且並不意欲以任何方式另外限制態樣及實施之範圍。實際上，為簡潔起見，系
統之習知製造、連接、製備及其他功能性態樣可不加以詳細描述。此外，各種圖中展示之連接線意欲表示各種元件之間的例示性功能性關係及/或實體耦合。許多替代或附加功能關係或實體連接可存在於實際系統中，及/或在一些具體例中可不存在。
應理解，本文中所述之組態及/或方法本質上為例示性的，且此等特定具體例或實施例不視為具有限制意義，原因在於可能存在諸多變化。本文中所描述之特定程序或方法可表示任何數目的處理程序策略中之一或多者。因此，所說明之各種動作可以所說明之順序、以其他順序進行，或在一些情況下被省略。
本發明之標的物包括本文中所揭示之各種製程、系統及組構以及其他特徵、功能、動作及/或特性，以及其任何及所有等效物的所有新穎但非顯而易見之組合及子組合。
100‧‧‧系統
110‧‧‧反應腔室
120‧‧‧基座
130‧‧‧噴淋頭
140‧‧‧遠端電漿單元
145‧‧‧輸送路徑
150‧‧‧基板
160‧‧‧第一氣體源
170‧‧‧第二氣體源
180‧‧‧第三氣體源
190‧‧‧第四氣體源
Claims (21)
- 一種用來加工半導體基板之裝置，其包括：反應腔室；基座，其經組構以固持基板；第一氣體源，其用來提供第一氣體；第二氣體源，其用來提供第二氣體；第一遠端電漿單元，其經組構以接收該第一氣體並產生第一自由基氣體；氣體分佈器件，其經組構以使該第一自由基氣體及該第二氣體於該基板上流動；及輸送路徑，其將該遠端電漿單元連接至該氣體分佈器件，其中該第一自由基氣體通過該氣體分佈器件至該基板上；其中該氣體分佈器件、該反應腔室、該輸送路徑、及該基座經塗布下列中之至少一者：陽極氧化氧化鋁(Al2O3)；原子層沉積(ALD)形成之氧化鋁；電漿噴霧Al2O3；具有天然氧化鋁之裸鋁部件；氧化釔(Y2O3)；經氧化釔穩定之氧化鋯(YSZ)；氧化鋯(ZrO2)；氧化鑭鋯(LZO)；釔鋁石榴石(YAG)；氧氟化釔(YOF)；氧化鋁(Al2O3)；氧化鋯(ZrO2)；氧化釔(Y2O3)；或經氧化釔穩定之氧化鋯(YSZ)，其中該第一自由基氣體包含氟自由基，且其中該第二氣體包含氫自由基。
- 如請求項1之裝置，其中該第一氣體包含以下中之至少一者：NF3、CF4、C2F6、C4F6、C4F8、COF2、SF6或WF6。
- 如請求項1之裝置，其中該第二氣體包含以下中之至少一者：H2、NH3、H2O、O2或O3。
- 如請求項1之裝置，其進一步包括：第三氣體源，其用來提供第三氣體；及 第四氣體源，其用來提供第四氣體。
- 如請求項4之裝置，其中該第三氣體包含NH3。
- 如請求項4之裝置，其中該第四氣體包含以下中之至少一者：氬、氦、氮或氖。
- 如請求項1之裝置，其中使用該第一氣體以自該基板移除氧化物。
- 如請求項1之裝置，其中使用該第二氣體以自該基板移除碳。
- 如請求項1之裝置，其中該第二氣體通過該第一遠端電漿單元並轉變成第二自由基氣體。
- 如請求項1之裝置，其進一步包括第二遠端電漿單元，其經組構以接收該第二氣體並產生第二自由基氣體。
- 如請求項1之裝置，其中該輸送路徑包括塊狀石英材料。
- 一種用於加工半導體基板之方法，其包含：提供如請求項1之裝置；於該基板上進行氧化物轉化步驟，該氧化物轉化步驟包括：(1)使第一氣體流入第一遠端電漿單元中以形成第一自由基氣體；及(2)使該第一自由基氣體於該基板上流動；於該基板上進行氧化物昇華步驟，該氧化物昇華步驟包括：(1)第一加熱步驟；及(2)第二加熱步驟；及於該基板上進行碳移除步驟；其中該氧化物轉化步驟、該氧化物昇華步驟、及該碳移除步驟各係於該反應腔室中進行；及其中視需要重複該氧化物轉化步驟、該氧化物昇華步驟、及該碳移除步驟中之任一者，其中該第一自由基氣體包含氟自由基，且 其中該第二氣體包含氫自由基。
- 如請求項12之方法，其中該碳移除步驟包括：使第二氣體流入該第一遠端電漿單元中以形成第二自由基氣體；及使該第二自由基氣體於該基板上流動。
- 如請求項12之方法，其中該碳移除步驟包括：使第二氣體流入第二遠端電漿單元中以形成第二自由基氣體；及使該第二自由基氣體於該基板上流動。
- 如請求項12之方法，其中該第一氣體包含以下中之至少一者：NF3、CF4、C2F6、C4F6、C4F8、COF2、SF6或WF6。
- 如請求項13之方法，其中該第二氣體包含以下中之至少一者：H2、NH3、H2O、O2或O3。
- 一種用於加工半導體基板之方法，其包含：提供如請求項1之裝置；於該基板上進行碳移除步驟；於該基板上進行氧化物轉化步驟，該氧化物轉化步驟包括：(1)使第一氣體流入第一遠端電漿單元中以形成第一自由基氣體；及(2)使該第一自由基氣體於該基板上流動；於該基板上進行氧化物昇華步驟，該氧化物昇華步驟包括：(1)第一加熱步驟；及(2)第二加熱步驟；及其中該碳移除步驟、該氧化物轉化步驟、及該氧化物昇華步驟各係於該反應腔室中進行；及其中視需要重複該碳移除步驟、該氧化物轉化步驟、及該氧化物昇華步驟中之任一者，其中該第一自由基氣體包含氟自由基，且 其中該第二氣體包含氫自由基。
- 如請求項17之方法，其中該碳移除步驟包括：使第二氣體流入該第一遠端電漿單元中以形成第二自由基氣體；及使該第二自由基氣體於該基板上流動。
- 如請求項17之方法，其中該碳移除步驟包括：使第二氣體流入第二遠端電漿單元中以形成第二自由基氣體；及使該第二自由基氣體於該基板上流動。
- 如請求項17之方法，其中該第一氣體包含以下中之至少一者：NF3、CF4、C2F6、C4F6、C4F8、COF2、SF6或WF6。
- 如請求項18之方法，其中該第二氣體包含以下中之至少一者：H2、NH3、H2O、O2或O3。
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| KR102651766B1 (ko) | 2024-03-28 |
| US20190019670A1 (en) | 2019-01-17 |
| KR20240035416A (ko) | 2024-03-15 |
| JP2019033249A (ja) | 2019-02-28 |
| CN109256315A (zh) | 2019-01-22 |
| KR20190008096A (ko) | 2019-01-23 |
| US20220367175A1 (en) | 2022-11-17 |
| TW201908027A (zh) | 2019-03-01 |
| JP2023085394A (ja) | 2023-06-20 |
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