TWI740979B - 使用蝕刻劑膜循環乾蝕刻之方法 - Google Patents

使用蝕刻劑膜循環乾蝕刻之方法 Download PDF

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TWI740979B
TWI740979B TW106123203A TW106123203A TWI740979B TW I740979 B TWI740979 B TW I740979B TW 106123203 A TW106123203 A TW 106123203A TW 106123203 A TW106123203 A TW 106123203A TW I740979 B TWI740979 B TW I740979B
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財津優
小林伸好
小林明子
堀勝
近藤博基
堤隆嘉
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荷蘭商Ａｓｍ智慧財產控股公司
國立大學法人名古屋大學
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Abstract

本發明係關於一種藉由乾蝕刻製程蝕刻基板上之靶層之方法，其包括至少一個蝕刻循環，其中蝕刻循環包括：使用反應性物質將含鹵素膜沉積至基板上之靶層上；以及使用非鹵素蝕刻氣體電漿蝕刻含鹵素膜，該電漿本身實質上不蝕刻靶層，以在含鹵素膜及靶層的邊界區域處產生蝕刻劑物質，從而蝕刻邊界區域中的部分靶層。

Description

使用蝕刻劑膜循環乾蝕刻之方法
本發明一般係關於循環乾蝕刻由矽或金屬氧化物、氮化物或碳化物構成之層之方法。
如日本專利公開案第2013-235912號及第2014-552104號中所揭示，原子層蝕刻(ALE)係為使用吸附在靶膜上的蝕刻劑氣體並且與激發的反應物質反應所進行的循環的原子層等級蝕刻。與習知的蝕刻技術相比，ALE可在次奈米級上執行精確的原子層等級連續蝕刻以形成精細的窄凹凸圖案，並且可適用於例如雙圖案化製程。作為蝕刻劑氣體，已知Cl2、HCl、CHF3、CH2F2、CH3F、H2、BCL3、SiCl4、Br2、HBr、NF3、CF4、C2F6、C4F8、SF6、O2、SO2、COS等。然而，此顯露了當蝕刻氧化物或氮化物礦物膜(諸如氧化矽或氮化矽膜)時，藉由ALE在基板上蝕刻膜的平面內均勻性(in-plane uniformity)並非令人滿意的。
當使用Cl2作為蝕刻劑氣體藉由ALE蝕刻Si或GaAs時，可獲得相對良好的蝕刻之平面內均勻性。然而，當使用氟碳化物(諸如C4F8)作為蝕刻劑氣體藉由ALE蝕刻氧化矽或氮化矽膜時，無法獲得良好的蝕刻之平面內均勻性。此係因為蝕刻劑氣體係通過物理吸附而非化學吸附被吸附至基板表面上，儘管事實上一般來說，蝕刻劑氣體的吸附有時被稱為「化 學吸附」。也就是說，習知的ALE藉由物理吸附至金屬或氧化矽或氮化矽膜表面上的蝕刻氣體蝕刻金屬或氧化矽或氮化矽膜，其中吸附的蝕刻劑氣體與激發的物質反應，並且亦藉由在被吹掃之後留在反應空間中的蝕刻劑氣體引起氣相蝕刻。結果，蝕刻之平面內均勻性受損。若蝕刻劑氣體被化學吸附至基板表面上，該吸附係為「化學吸附」，其係為化學飽和吸附，其係自限制性吸附反應製程，其中沉積的蝕刻劑氣體分子之量係藉由反應性表面位點之數量而測定並且與飽和後的前驅物曝露無關，並且蝕刻劑氣體的供應使得每循環反應性表面位點飽和(即，每循環的吸附在表面上的蝕刻劑氣體原則上具有單分子厚度)。當發生蝕刻劑氣體在基板表面上化學吸附時，可實現高的蝕刻之平面內均勻性。習知的ALE，即使稱之為「化學吸附」的吸附，實際上係藉由物理吸附將蝕刻劑氣體吸附至基板表面(例如SiO2及SiN)上。若蝕刻劑氣體的吸附係化學吸附，蝕刻之平面內均勻性邏輯上應係高的，並且每循環的蝕刻速率在表面被蝕刻劑氣體分子飽和後亦應不受蝕刻劑氣體的流速或蝕刻劑氣體流之脈衝之持續時間影響。然而，習知的蝕刻劑氣體皆不符合上文。
本發明所包括的上文及任何關於相關技術的問題及解決方法的其他討論僅用於為本發明提供上下文之目的，不應被視為承認任何或所有討論在本發明提出時係已知的。
在一些具體實例中，將由蝕刻劑之組分所構成之膜(其可被稱為「蝕刻劑膜」)沉積至靶層表面上，然後，使用電漿處理蝕刻蝕刻劑膜以及靶層。藉由進行沉積步驟及蝕刻步驟並根據需要交替重複該等步驟， 可在進行沉積步驟及蝕刻步驟作為蝕刻循環的每個時刻以實質上恆定的預定量蝕刻靶層。在上文中，蝕刻劑組分最初不用作蝕刻靶層的蝕刻劑氣體，而是在靶層表面上形成膜。在一些具體實例中，「膜」係指沿著垂直於厚度方向的方向連續延伸之層，實質上沒有針孔以覆蓋整個靶或靶的有關表面，並且膜典型地係通過使用反應性物質的反應所形成，而非僅係藉由表面上的氣體分子的化學或物理吸附所形成；因此，隨著沉積製程的繼續，膜可在厚度方向上生長超過原子層厚度。
在一些具體實例中，當沉積在靶層表面上的蝕刻劑膜被諸如氧電漿的反應性離子蝕刻時，蝕刻劑膜的組分被解離並且與反應性離子反應，產生反應性蝕刻劑物質，其可蝕刻在蝕刻劑膜與靶層之間的邊界處的部分靶層。在上文中，由於需要在邊界附近產生反應性蝕刻劑物質，所以在邊界處僅有一定厚度的蝕刻劑膜可有助於靶層的蝕刻反應。此外，由於蝕刻蝕刻劑膜的反應性離子不蝕刻靶層，當蝕刻劑膜被反應離子移除時，靶層的蝕刻反應停止。因此，藉由上述方法，可總是藉由一個蝕刻循環蝕刻恆定量的靶層，因此蝕刻製程的可控性及可操作性高。
例如，當靶層係由SiO2構成時，藉由電漿增強CVD或熱CVD在靶層表面上沉積氟碳化物膜(CF膜)作為蝕刻劑膜，然後將蝕刻劑膜暴露於氧電漿，以便移除蝕刻劑膜並且同時蝕刻靶層表面。在上文中，「同時」係指實質上或主要同時發生或實質上或主要以時間重疊的方式發生。在上文中，靶層的蝕刻部分的深度隨著蝕刻劑膜的厚度增加而增加；然而，當蝕刻劑膜的厚度達到一定值時，蝕刻部分的深度達到平線區並且不再增加。同樣地，靶層的蝕刻部分的深度隨著蝕刻劑膜暴露於電漿的持續時間 增加而增加；然而，當蝕刻劑膜暴露於電漿的持續時間達到一定值時，蝕刻部分的深度達到平線區並且不再增加。也就是說，在一些具體實例中，上面討論的蝕刻製程係為包括具有飽和點的兩個參數的自限制性反應製程。
在上文中，CF膜係藉由氧電漿以氣體(諸如CFx，COFx，COx等)方式移除，並且在SiO2層表面附近的區域中，部分SiO2層亦同時以氣體(諸如SiFx，COx等)方式移除。僅接近邊界的部分CF膜有助於移除部分SiO2層，CF膜的剩餘部分並不有助於移除SiO2層，而是僅被氧電漿移除。因此，SiO2層的蝕刻部分的深度相對於CF膜的厚度達到平線區。並且，由於使用氧電漿蝕刻SiO2層僅在存在CF膜時有效，所以當移除(用盡)CF膜時，停止蝕刻SiO2層，即SiO2層的蝕刻部分的深度相對於氧電漿暴露的持續時間亦達到平線區。
在一些具體實例中，靶層可由可使用氟蝕刻(即藉由使用CF膜)的任何材料(例如，TiO2)所構成。在一些具體實例中，只要選擇適合的蝕刻劑膜，靶層可由可使用氟以外的鹵素蝕刻的材料所構成。典型地，蝕刻劑膜在反應性離子蝕刻(RIE)製程中暴露於氧電漿。由於蝕刻製程涉及自限制性反應製程(或飽和製程)，因此可實現高可控性。
為了總結本發明之觀點及相對於相關先前技術所達成的優點，本發明描述了本發明的某些目的及優點。當然，應當理解，不一定所有此等目的或優點都可根據本發明的任何特定具體實例而實現。因此，例如，發明所屬技術領域中具有通常知識者會了解本發明可以實現或最佳化本文教示的一個優點或一組優點的方式來體現或實施，而不必實現如本文 可教示或建議的其它目的或優點。
從下面的詳細描述中，本發明的其它觀點、特徵及優點會係係為顯而易見的。
1‧‧‧基板
2‧‧‧導電平板電極
3‧‧‧反應腔室
4‧‧‧導電平板電極
5‧‧‧傳送腔室
6‧‧‧排氣管線
7‧‧‧排氣管線
11‧‧‧反應區
12‧‧‧接地
13‧‧‧環形管道
14‧‧‧分離板
16‧‧‧傳送區
20‧‧‧HRF功率
21‧‧‧氣體管線
22‧‧‧氣體管線
23‧‧‧氣體管線
24‧‧‧氣體管線
41‧‧‧基板
42‧‧‧靶層
43‧‧‧含鹵素膜(蝕刻劑膜)
44‧‧‧邊界區域
45‧‧‧靶層
T1‧‧‧飽和厚度
T2‧‧‧深度
現在將參考旨在說明而非限制本發明的較佳具體實例的圖式來描述本發明的此等及其它特徵。圖式係大量簡化以用於所示之目的，並且不一定按比例繪製。
圖1係為可用於本發明具體實例之電漿輔助循環蝕刻儀器之示意圖示。
圖2展示根據本發明具體實例之在一個循環中電漿輔助循環蝕刻的示意性製程程序，其中程序中所示之步驟表示ON狀態，而程序中並無所示之步驟係表示OFF狀態，每個ON及OFF狀態之長度不表示每個製程的持續時間。
圖3說明根據本發明具體實例之一個循環的蝕刻製程的示意圖，其中(a)表示沉積步驟，(b)表示預蝕刻步驟，以及(c)表示蝕刻步驟。
圖4係為展示根據本發明具體實例之每循環的蝕刻速率(EPC)(
Figure 106123203-A0101-12-0005-10
/循環)與每循環的沉積時間(秒)之間的關係的圖式。
圖5係為展示根據本發明具體實例之每循環的蝕刻速率(EPC)(
Figure 106123203-A0101-12-0005-11
/循環)與每循環的蝕刻時間(秒)之間的關係的圖式。
圖6係為展示根據本發明具體實例之SiO2層的厚度(nm)與蝕刻製程中重複的循環次數之間的關係的圖式。
在本發明中，「氣體」可包括汽化的固體及/或液體，並且可由單一氣體或氣體混合物構成。在本發明中，通過噴頭引入至用於沉積的反應腔室的製程氣體可包含以下，或基本上由以下組成：蝕刻劑氣體以及添加劑氣體。添加劑氣體典型地包括用於稀釋蝕刻劑氣體並且在處於激發態時與蝕刻劑氣體反應的稀釋氣體。蝕刻劑氣體可與載體氣體(諸如惰性氣體)一起引入。並且，除了處理氣體之外的氣體，即不經過噴頭引入的氣體，可用於例如密封包括密封氣體(諸如惰性氣體)的反應空間。在一些具體實例中，用語「蝕刻劑氣體」通常係指至少一種參與蝕刻反應的氣態或汽化化合物，該蝕刻反應蝕刻基板上的靶層，且特別係指至少一種在激發態中在靶層上沉積且在被電漿活化時蝕刻靶層的化合物。用語「反應物氣體」係指至少一種有助於沉積蝕刻劑膜、活化蝕刻劑膜或者藉由蝕刻劑膜的組分催化蝕刻反應的氣態或汽化化合物。反應物氣體可用作吹掃氣體。稀釋氣體及/或載體氣體可用作「反應物氣體」。用語「載體氣體」係指處於非激發態的惰性或非活性氣體，其在混合態中攜帶蝕刻劑氣體至反應空間，並且作為包括蝕刻劑氣體的混合氣體進入反應空間。
此外，在本發明中，當可行範圍可依據例行工作來測定時，變數的任何兩個數字可構成變數的可行範圍，並且所指的任何範圍可包括或排除端點。此外，所指的變數的任何值(不管其是否用「約」表示)可指精確值或近似值並且包括等同物，並且在一些具體實例中可指平均值、中值、代表值、多數等。此外，用語「由...構成」及「具有」在一些具體實例中係獨立地指「典型地或廣泛地包含」、「包含」、「基本上由...組成」或「由... 組成」。此外，冠詞「一(a、an)」係指包括多種物種的物種或屬。在本發明中，任何定義的含義在一些具體實例中不一定排除普通及慣用的含義。
在本發明中沒有具體說明條件及/或結構的情況下，發明所屬技術領域中具有通常知識者可容易地以例行實驗鑑於本發明提供該等條件及/或結構。在所有揭示的具體實例中，為了預期的目的，具體實例中所使用的任何元件可用等同於其的任何元件替代，包括本文明確地、必須地或本質地揭示的該等元件。此外，本發明可同樣地適用於裝置及方法。
將參考較佳具體實例說明具體實例。然而，本發明不限於較佳具體實例。
一些具體實例提供一種藉由乾蝕刻製程蝕刻基板上之靶層之方法，其包含至少一個蝕刻循環，其中蝕刻循環包含：(i)使用反應性物質將含鹵素膜沉積至基板上之靶層上，其中含鹵素膜與靶層彼此接觸；以及(ii)使用非鹵素蝕刻氣體電漿蝕刻含鹵素膜，該電漿本身實質上不蝕刻靶層，以在含鹵素膜及靶層的邊界區域處產生蝕刻劑物質，從而蝕刻邊界區域中的部分靶層。在步驟(i)中，含鹵素膜亦稱為蝕刻劑膜，且用於將含鹵素膜沉積的含鹵素氣體亦稱為蝕刻劑氣體。步驟(i)中的「反應性物質」實質上不蝕刻靶層，而是在靶層上形成蝕刻劑膜。在本發明中，「實質上為零」或類似語(例如，「實質上不蝕刻」)可指不重要之量、小於可檢測量之量、不明顯影響靶或預期的性質之量、或發明所屬技術領域中具有通常知識者所認知幾乎為零之量，諸如在一些具體實例中相對於總數或參考值小於10%、小於5%、小於1%或其任何範圍。
在一些具體實例中，靶層係由矽或金屬氧化物、氮化物或碳 化物構成，其中金屬可為Ri、W、Ta等，諸如SiO2、SiN、SiC、TiO2等。當蝕刻劑氣體含有Cl或Br時，靶層可由Al2O3、AlN、GaAs、GaN、GaP、InP等構成。在一些具體實例中，當蝕刻劑氣體含有Cl時，靶層可由聚氯乙烯構成。發明所屬技術領域中具有通常知識者可依需根據例行實驗測定蝕刻劑氣體及靶層的可能組合。在一些具體實例中，靶層係藉由電漿增強CVD、熱CVD、循環CVD、電漿增強ALD、熱ALD、自由基增強ALD或任何其它薄膜沉積方法在包括側壁及底表面的溝槽或通孔中及/或平坦表面上所形成。典型地，靶層的厚度係為約50nm至約500nm範圍內(根據膜的應用及目的等可以認為合適地選擇所需的膜厚度)。
在一些具體實例中，在步驟(i)中，藉由氣相反應將含鹵素膜沉積，其中反應性物質係為蝕刻劑氣體或由鹵素及碳構成之氣體。在一些具體實例中，鹵素係為F、Cl或Br。在一些具體實例中，可使用包括習知蝕刻劑氣體(例如，在「先前技術」段落中所討論的蝕刻劑氣體)的任何適合的蝕刻劑氣體。由於步驟(i)中的蝕刻劑氣體不用作直接蝕刻靶層的反應性蝕刻氣體，而是用作用於沉積的氣體，較佳地，蝕刻劑氣體係為具有雙鍵或三鍵的CxFy，其中x及y為整數，且x為至少2，例如，C2F2、C2F4、C3F6、C4F8、C5F8、C5F10或前述的任何組合。此等氣體傾向容易形成處於激發態的氟聚合物。在步驟(i)中，選擇反應物氣體以沉積蝕刻劑膜，而非蝕刻靶層，例如，不使用含氧氣體，其係因為氧電漿產生來自蝕刻劑氣體的活性蝕刻物質以蝕刻氧化矽膜或類似物。在一些具體實例中，反應物氣體係為惰性氣體，諸如Ar及He。在一些具體實例中，藉由選擇適合的反應物氣體及其它沉積條件，可使用通常用於蝕刻氧化矽膜(諸如CF4、 C2F6、C3F8、C4F10等)的蝕刻劑氣體。
在一些具體實例中，除了含氟的蝕刻劑氣體之外的蝕刻劑氣體可在步驟(i)中用於沉積蝕刻劑膜。例如，可使用烷基鹵化物(諸如C2H3Cl)。此外，SF6、HCl、HBr等可與烴(諸如CH4)組合使用。
在一些具體實例中，可藉由諸如原子層沉積(ALD)的表面反應將蝕刻劑膜沉積，其中蝕刻劑氣體化學吸附至靶層表面上，然後將表面暴露於反應物氣體的反應性物種。
在一些具體實例中，步驟(i)使用氣相反應，該氣相反應係為電漿增強CVD。在一些具體實例中，電漿增強CVD包含：(a)將惰性氣體連續供給至其中放置基板的反應空間；(b)將含鹵素氣體連續供給至反應空間；以及(c)在經過步驟(a)及(b)之預設持續時間且沒有激發惰性氣體及含鹵素氣體之後，施加RF功率(RF power)至反應空間以將含鹵素膜沉積至靶層上，其中在步驟(i)至(iii)中，沒有氧化氣體被供給至反應空間。在上文中，用語「連續」係指在空間中不中斷(例如，不中斷地供應至基板上)、在流中不中斷(例如，不中斷地流入)及/或在恆定速率下(該用語不需同時滿足所有前述定義)，其取決於具體實例。在一些具體實例中，「連續」流具有恆定的流速(或者，甚至該流係為「連續的」，其流速可隨時間而改變)。在一些具體實例中，步驟(c)的持續時間短於步驟(a)及(b)的預設持續時間。由於RF功率係在短時間內施加至反應空間用於沉積，因此在施加RF功率之前，必須將含鹵素氣體完全填充於反應空間中。
在一些具體實例中，步驟(i)繼續進行直到含鹵素膜的厚 度落在0.5nm至10nm、較佳1nm至5nm範圍內，該等範圍接近平線區厚度(或飽和厚度)，超過此範圍即使進一步增加含鹵素膜的厚度，步驟(ii)中靶層的蝕刻量也不會增加。
在一些具體實例中，步驟(i)的持續時間與靶層的蝕刻部分的厚度相關直到靶層的蝕刻部分的厚度達到平線區，而步驟(i)的持續時間增加，步驟(i)繼續進行直到靶層的蝕刻部分的厚度達到平線區或達到接近平線區的點。本發明上文已討論上述機制，儘管該等機制並不旨在限制本發明。
在一些具體實例中，步驟(ii)繼續進行直到含鹵素膜實質上完全被蝕刻，此表示靶層的邊界區域實質上全部部分被蝕刻。在上文中，「實質上全部」或類似語可指以以下表示整體短缺：不重要之量、小於可檢測量之量、不明顯影響靶或預期的性質之量、或發明所屬技術領域中具有通常知識者所認知為無關緊要之值之量，諸如在一些具體實例中相對於總數或參考值小於10%、小於5%、小於1%或其任何範圍。較佳地，步驟(ii)繼續進行直到含鹵素膜完全被蝕刻，此表示靶層的邊界區域的全部部分完全被移除。靶層的「邊界區域」係定義為當含鹵素膜完全被蝕刻時被蝕刻的區域。當含鹵素膜的殘餘物殘留在靶層表面上時，殘留物會至少部分地干擾靶層的蝕刻，影響靶層的蝕刻深度的平面內均勻性。
在一些具體實例中，在步驟(ii)中，靶層的蝕刻部分的厚度為0.1nm至2.0nm、較佳為0.5nm至1.0nm，其厚度大於原子層蝕刻(ALE)中所定義的單層厚度，其小於0.1nm/循環。
在一些具體實例中，在步驟(ii)中，非鹵素蝕刻氣體係為 氧。然而，可選擇任何適合的反應物氣體來活化蝕刻劑膜，以藉由反應性離子蝕刻蝕刻靶層。在一些具體實例中，諸如Ar及He氣體的惰性氣體、氫氣或氮氣可單獨作為反應物氣體來使用或與氧氣組合使用。
在一些具體實例中，在步驟(ii)中，藉由反應性離子蝕刻(RIE)蝕刻含鹵素膜。RIE可為感應耦合電漿蝕刻或電容耦合電漿蝕刻。在一些具體實例中，電容耦合電漿蝕刻包含：(a)將反應物氣體連續供給至其中放置基板的反應空間；及(b)在經過步驟(a)之預設持續時間且沒有激發反應物氣體之後，施加RF功率至反應空間以蝕刻含鹵素膜及靶層。
在一些具體實例中，包含步驟(i)及(ii)的蝕刻循環重複至少兩次直到獲得所需的靶層的蝕刻深度。由於蝕刻循環係為自限制性蝕刻製程或飽和製程，因此靶層的蝕刻深度與執行的循環次數成比例。
在一些具體實例中，步驟(i)及步驟(ii)係在相同的反應腔室中連續進行。在上文中，用語「連續」係指以下之至少一者：不破壞真空、不暴露於空氣中、不打開腔室、作為原位製程、不中斷地作為順序中的步驟、不改變製程條件，以及不在步驟之間在基板表面上引起化學變化，其取決於具體實例。在一些具體實例中，諸如上下文中的吹掃或其他可忽略的步驟的輔助步驟不被視為步驟，因此，用語「連續」不排除插入輔助步驟。
參照附圖說明一些具體實例，但並非旨在限制本發明。
圖3說明根據本發明具體實例之一個循環的蝕刻製程的示意圖，其中(a)表示沉積步驟，(b)表示預蝕刻步驟，以及(c)表示蝕刻步驟。在沉積步驟(步驟(a))之前，在反應空間中提供在其上形成有靶 層42的基板41(例如，矽晶圓或其它半導體晶圓)。在沉積步驟中，將含鹵素膜(蝕刻劑膜)43以不小於飽和厚度T1的厚度沉積至靶層42上，其中含鹵素膜43及靶層42彼此接觸。飽和厚度T1係定義為一厚度，超過其的蝕刻劑膜的部分不會有助於靶層的蝕刻，即，即使蝕刻劑膜的厚度進一步增加超過飽和厚度T1，靶層的蝕刻量也不會增加。在預蝕刻步驟(步驟(b))中，將蝕刻劑膜43暴露於電漿(諸如氧電漿)中，從而蝕刻蝕刻劑膜，產生諸如CFx、COFx、COx等的氣體組分，以及移除蝕刻劑膜43高於飽和厚度T1的頂部部分。當進行蝕刻劑膜43的蝕刻並且蝕刻劑膜43被蝕刻至飽和厚度T1時，來自蝕刻劑膜43的諸如CFx、COFx、COx等的氣體組分同時藉由在邊界區域44處使用氧電漿通過以下化學反應自具有深度T2的部分靶層42產生諸如SiFx、COx等的氣體組分，例如：SiO2+CFx+O * → SiFx+COx+COFx
邊界區域44係由具有飽和厚度T1的蝕刻劑膜43的邊界區域及具有深度T2的靶層42的邊界區域所構成。邊界區域的總厚度(T1+T2)可取決於電漿中的離子能量，例如取決於RF功率及反應空間的壓力。邊界區域44可由由諸如SiCOF等的混合組分所構成的中間體所組成。在蝕刻步驟(步驟(c))中，邊界區域或中間體層44係作為氣體組分被移除，其中蝕刻靶層42至深度T2以獲得經蝕刻的靶層45。應當注意，儘管步驟(b)及(c)係分別顯示以用於容易理解步驟的原理，該等步驟係相當同時發生的。由於電漿本身實質上不蝕刻靶層，所以當移除邊界區域44時，靶層45的蝕刻停止。
在一些具體實例中，可如圖2所示設置製程程序。圖2展示 根據本發明具體實例之在一個循環中電漿輔助循環蝕刻的示意性製程程序，其中程序中所示之步驟表示ON狀態，而程序中並無所示之步驟係表示OFF狀態，每個ON及OFF狀態之長度不表示每個製程的持續時間。在此具體實例中，一個蝕刻循環包含沉積步驟及蝕刻步驟。沉積步驟包含「吹掃」及「步驟1」，且蝕刻步驟包含「吹掃」及「步驟2」。在沉積步驟的「吹掃」中，將稀釋氣體(諸如Ar及/或He)連續供給至其中放置基板的反應空間，同時將含鹵素氣體連續供給至反應空間中，而不施加RF功率並且不供給氧化氣體。在經過預設的「吹掃」持續時間之後，在沉積步驟的「步驟1」中，將RF功率施加至反應空間以將含鹵素膜沉積至靶層上，而不供給氧化氣體。在「步驟1」之後，開始蝕刻步驟的「吹掃」，其中將氧化氣體(反應物氣體)連續供給至反應空間，而不供給稀釋氣體及含鹵素氣體並且不施加RF功率。在經過預設的「吹掃」持續時間之後，將RF功率施加至反應空間以蝕刻含鹵素的膜及靶層。可重複此蝕刻循環直到蝕刻至所需的靶層的蝕刻深度。
在一些具體實例中，可使用遠端電漿單元來製造稀釋氣體的反性應物種及/或反應物氣體的反性應物種，其中圖2所示之程序中的「RF」係由自遠端電漿單元引入稀釋氣體自由基或引入反應物氣體自由基來替代。在一些具體實例中，RF功率係以脈衝施加。
在一些具體實例中，蝕刻循環可在下面表1所示的條件下進行。
在圖2所示之程序中，可使用可連續供給至反應空間的載體氣體來提供含鹵素氣體，特別是當含鹵素氣體係為諸如C5F8、C5F10等的液體材料的汽化氣體時。此可使用流通切換(flow-pass switching；FPS)系統(例如，2015年8月18日提交之美國專利申請案第14/829,565號所揭示之系統，其全部內容以引用方式併入本文中)來實現，其中載體氣體管線係設置有具有前驅物儲存器(瓶)的繞行管線，並且切換主管線及繞行管線，其中當欲僅將載體氣體供給至反應腔室時，繞行管線閉合，而當欲將載體氣體及前驅物氣體兩者供給至反應腔室時，主管線閉合，並且載體氣體流過繞 行管線並與前驅物氣體一起自瓶中流出。以此種方式，載體氣體可連續流入反應腔室，並且可藉由切換主管線及繞行管線以脈衝方式來攜帶前驅物氣體。
可使用例如包括圖1所示之儀器的任何適合的儀器來執行製程循環。圖1係為電漿輔助循環蝕刻儀器之示意圖示，意欲與被編程用於進行下文描述的程序的控制相結合，可用於本發明的一些具體實例。在該圖中，藉由在反應腔室3的內部11(反應區)中並聯且面對彼此地提供一對導電平板電極4、2，將HRF功率(13.56MHz或27MHz)20施加至一側，並且電接地另一側12，電漿在電極之間被激發。溫度調節器設置在下層2(下電極)中，並且放置於其上的基板1的溫度在給定溫度下保持恆定。上電極4也用作噴淋板(shower plate)，並且將惰性氣體、反應物氣體及蝕刻劑氣體分別通過氣體管線21、22及23並且通過噴淋板4引入至反應腔室3中。此外，在反應腔室3中設置有具有排氣管線7的環形管道13，反應腔室3的內部11中的氣體通過其被排出。此外，將稀釋氣體通過氣體管線23引入至反應腔室3中。此外，設置在反應腔室3下方的傳送腔室5設置有密封氣體管線24，以將密封氣體經由傳送腔室5的內部16(傳送區)引入至反應腔室3的內部11中，其中傳送腔室5設置有用於分離反應區及傳送區的分離板14(該圖省略了將晶圓通過其傳送至傳送腔室5中或通過其自傳送腔室5中傳送出來的閘閥)。傳送腔室亦設置有排氣管線6。在一些具體實例中，多元素膜的沉積及表面處理係在相同的反應空間中進行，使得所有步驟可連續進行而不將基板暴露於空氣或其他含氧氛圍。在一些具體實例中，可使用遠端電漿單元來激發氣體。
在一些具體實例中，可使用雙腔室反應器(用於處理彼此緊密配置的晶圓的兩個部分或隔室)，其中反應物氣體及惰性氣體可通過共用管線來供應，而前驅物氣體係通過非共用管線來供應。在一些具體實例中，沉積步驟可使用與蝕刻步驟不同的儀器來執行。
發明所屬技術領域中具有通常知識者會理解，儀器包括一或多個控制器(未出示)，其被編程或以其他方式經組態以發生描述於本文其他地方的欲進行的沉積及反應器清潔製程。如發明所屬技術領域中具有通常知識者會理解的，控制器係與反應器的各種電源、加熱系統、泵、機器人系統及氣體流量控制器或閥連通。
參照下面的工作實施例進一步說明本發明。然而，該等實施例並不旨在限制本發明。在沒有具體說明條件及/或結構的實施例中，發明所屬技術領域中具有通常知識者可容易地以例行實驗鑑於本發明提供該等條件及/或結構。並且，在一些具體實例中，在具體實施例中應用的數字可被修改至少±50%範圍，並且該等數字係為近似值。
實施例
實施例1
藉由PEALD在300mm基板上形成厚度為24nm的氧化矽膜。在實施例1中，使用圖1所示之電漿輔助蝕刻儀器，在下面表2所示的條件下進行蝕刻劑膜的沉積及氧化矽膜的蝕刻。在每個蝕刻循環中所使用的程序如圖2所示。
將包含沉積步驟及蝕刻步驟的蝕刻循環重複3、6或9次。在實施例1中，當蝕刻劑膜的沉積時間(供給時間)改變時，測定每循環的蝕刻速率(etching rate per cycle；EPC)。結果如圖4所示。圖4係為展示實施例1中每循環的蝕刻速率(EPC)(
Figure 106123203-A0101-12-0017-12
/循環)與每循環的沉積時間(秒)之間的關係的圖式，其中繪製的EPC值係為當將蝕刻循環重複3、6及9次時所獲得的EPC平均值。
圖4表示隨著蝕刻劑膜的厚度(「沉積時間[s]」)增加，氧化矽層的蝕刻部分的深度(「每循環蝕刻[
Figure 106123203-A0101-12-0017-13
/cyc]」)增加；然而，蝕刻部分的深度達到接近平線區的點，該點被定義為即使當蝕刻劑膜的厚度增加時蝕刻 部分的深度也不再增加的點。此係因為蝕刻反應僅發生在邊界區域，並且邊界區域上方的部分蝕刻劑膜不會有助於蝕刻反應。在上文中，原則上，「接近平線區的點」可被定義為與其中蝕刻部分的深度隨著蝕刻劑膜的厚度增加而以高速率增加的高反應性區域或與高反應性區域與低反應性區域之間的中間區域相比，其中蝕刻部分的深度隨著蝕刻劑膜的厚度增加而以低速率增加的低反應性區域內的點。在圖4中，平線區被認為為約9
Figure 106123203-A0101-12-0018-14
/循環，其對應於約7秒的沉積時間，以及接近平線區的點被認為為約7.9
Figure 106123203-A0101-12-0018-16
/循環，其對應於約2秒的沉積時間。在一些具體實例中，參考沉積時間的「接近平線區的點」為平線區的80%或高於80%處的點。
實施例2
除了將沉積時間(「RF」(步驟1)的持續時間)設定為2秒之外，根據上述實施例1在實施例2中進行蝕刻製程，以及將蝕刻時間(「RF」(步驟2)的持續時間)如圖5所示變化。圖5係為展示在實施例2中每循環的蝕刻速率(EPC)(
Figure 106123203-A0101-12-0018-17
/循環)與每循環的蝕刻時間(秒)之間的關係的圖式。
圖5表示隨著蝕刻時間(「蝕刻時間[s]」)增加，氧化矽層的蝕刻部分的深度(「每循環的蝕刻[
Figure 106123203-A0101-12-0018-18
/循環]」)增加；然而，蝕刻部分的深度達到接近平線區的點，該點被定義為即使當蝕刻時間增加時蝕刻部分的深度也不再增加的點。此係因為只有當存在蝕刻劑膜時才發生蝕刻反應，並且當移除蝕刻劑膜時蝕刻停止。在上文中，原則上，「接近平線區的點」可被定義為與其中蝕刻部分的深度隨著蝕刻時間增加而以高速率增加的高反應性區域或與高反應性區域與低反應性區域之間的中間區域相比，其中蝕 刻部分的深度隨著蝕刻時間增加而以低速率增加的低反應性區域內的點。在圖5中，平線區被認為為約8
Figure 106123203-A0101-12-0019-19
/循環，其對應於約125秒的蝕刻時間，以及接近平線區的點被認為為約7.9
Figure 106123203-A0101-12-0019-20
/循環，其對應於約60秒的蝕刻時間。在一些具體實例中，參考蝕刻時間的「接近平線區的點」為平線區的90%或高於90%處的點。
實施例3
除了將沉積時間(「RF」(步驟1)的持續時間)設定為2秒之外，根據上述實施例1在實施例3中進行蝕刻製程，將蝕刻時間(「RF」(步驟2)的持續時間)設定為60秒，以及將蝕刻循環次數如圖6所示重複變化。圖6係為展示在實施例3中SiO2層的厚度(nm)與蝕刻製程中重複的循環次數之間的關係的圖式。
圖6表示蝕刻劑膜的厚度氧化矽層的蝕刻部分的深度(「SiO2厚度(nm)」)與蝕刻循環次數(「循環次數」)的增加成比例地降低。上述兩者之間的關係實質上係為線性的。也就是說，由於蝕刻製程使用自限制性或飽和製程，蝕刻製程的可控性非常高。
發明所屬技術領域中具有通常知識者會理解，在不脫離本發明精神的情況下，可進行許多及各種修改。因此，應當清楚地理解，本發明的形式僅係為說明性的，並不旨在限制本發明的範圍。
1‧‧‧基板
2‧‧‧導電平板電極
3‧‧‧反應腔室
4‧‧‧導電平板電極
5‧‧‧傳送腔室
6‧‧‧排氣管線
7‧‧‧排氣管線
11‧‧‧反應區
12‧‧‧接地
13‧‧‧環形管道
14‧‧‧分離板
16‧‧‧傳送區
20‧‧‧HRF功率
21‧‧‧氣體管線
22‧‧‧氣體管線
23‧‧‧氣體管線
24‧‧‧氣體管線

Claims (16)

  1. 一種藉由乾蝕刻製程蝕刻基板上之靶層之方法，其包含至少一個蝕刻循環，其中蝕刻循環包含：(i)使用反應性物質將含鹵素膜沉積至該基板上之該靶層上，其中該含鹵素膜與該靶層彼此接觸；以及(ii)使用非鹵素蝕刻氣體電漿蝕刻該含鹵素膜，該電漿本身實質上不蝕刻該靶層，以在該含鹵素膜及該靶層的邊界區域處產生蝕刻劑物質，從而蝕刻該邊界區域中的部分該靶層，其中在步驟(i)中，藉由氣相反應將該含鹵素膜沉積，其中該反應性物質係為蝕刻劑氣體或由鹵素及碳所構成之氣體，且其中該鹵素係為Cl或Br。
  2. 根據申請專利範圍第1項之方法，其中步驟(ii)繼續進行直到該含鹵素膜實質上完全被蝕刻，此表示該靶層的該邊界區域實質上全部部分被蝕刻。
  3. 根據申請專利範圍第1項之方法，其中步驟(i)的持續時間與該靶層的蝕刻部分的厚度相關直到該靶層的蝕刻部分的厚度達到平線區，而步驟(i)的持續時間增加，步驟(i)繼續進行直到該靶層的蝕刻部分的厚度達到平線區或達到接近平線區的點。
  4. 根據申請專利範圍第1項之方法，其中該蝕刻循環重複至少兩次。
  5. 根據申請專利範圍第1項之方法，其中步驟(i)繼續進行直到該含鹵素膜的厚度落在0.5nm至10nm範圍內。
  6. 根據申請專利範圍第1項之方法，其中在步驟(ii)中，該靶層的蝕刻 部分的厚度為0.1nm至2.0nm。
  7. 根據申請專利範圍第1項之方法，其中該蝕刻劑氣體係為烷基鹵化物氣體。
  8. 根據申請專利範圍第1項之方法，其中該氣相反應係為電漿增強CVD。
  9. 根據申請專利範圍第8項之方法，其中該電漿增強CVD包含：(a)將惰性氣體連續供給至其中放置該基板的反應空間；(b)將該含鹵素氣體連續供給至該反應空間；以及(c)在經過步驟(a)及(b)之預設持續時間且沒有激發該惰性氣體及該含鹵素氣體之後，施加RF功率(RF power)至該反應空間以將該含鹵素膜沉積至該靶層上，其中在步驟(a)至(c)中，沒有氧化氣體被供給至該反應空間。
  10. 根據申請專利範圍第9項之方法，其中步驟(c)的持續時間短於步驟(a)及(b)的預設持續時間。
  11. 根據申請專利範圍第1項之方法，其中在步驟(ii)中，該非鹵素蝕刻氣體係為氧。
  12. 根據申請專利範圍第1項之方法，其中在步驟(ii)中，藉由反應性離子蝕刻(RIE)蝕刻該含鹵素膜。
  13. 根據申請專利範圍第12項之方法，其中該RIE為電容耦合電漿蝕刻。
  14. 根據申請專利範圍第13項之方法，其中該電容耦合電漿蝕刻包含：(a)將反應物氣體連續供給至其中放置該基板的反應空間；及(b)在經過步驟(a)之預設持續時間且沒有激發該反應物氣體之後，施加RF功率至該反應空間以蝕刻該含鹵素膜及該靶層。
  15. 根據申請專利範圍第1項之方法，其中該靶層係由SiO2、SiN或SiC所構成。
  16. 根據申請專利範圍第1項之方法，其中步驟(i)及步驟(ii)係在相同的反應腔室中連續進行。
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