TW202119494A - 基板處理方法 - Google Patents

基板處理方法 Download PDF

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TW202119494A
TW202119494A TW109132531A TW109132531A TW202119494A TW 202119494 A TW202119494 A TW 202119494A TW 109132531 A TW109132531 A TW 109132531A TW 109132531 A TW109132531 A TW 109132531A TW 202119494 A TW202119494 A TW 202119494A
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layer
plasma
film
gas
processing method
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姜熙成
閔允基
林完奎
吳錫宰
曺成日
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荷蘭商Ａｓｍ Ｉｐ私人控股有限公司
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Abstract

一種基板處理方法，其能夠實現形成在階梯結構上的薄膜的整個厚度範圍中的均勻的蝕刻選擇性，此方法包括：藉由執行多個迴圈而在基板上形成薄膜，迴圈包括形成至少一層以及在第一處理條件下將電漿施加到至少一層；以及在不同於第一處理條件的第二處理條件下將電漿施加到薄膜。

Description

基板處理方法
一或多個實施例有關於一種基板處理方法，更具體地，有關於一種可以改善形成在階梯結構（stepped structure）上的薄膜的蝕刻選擇性的基板處理方法。
隨著半導體圖案結構的小型化和三維化，越來越需要可以簡化製程的新型薄膜沉積技術。例如，3D NAND快閃記憶體裝置具有垂直堆疊的柵極結構和電極佈線結構。為了使這些結構互連，需要選擇性地去除沉積在階梯結構上的膜，以形成墊結構（pad structure）的技術。
為了選擇性地去除沉積在階梯結構上的膜，藉由電漿製程將膜沉積在階梯結構上，然後對膜進行濕式蝕刻，以去除階梯結構的側部膜，從而留下階梯結構的上部膜和下部膜。然而，也可以使用去除階梯結構的上部膜和下部膜並留下階梯結構的側部膜的方法。
此方法可以藉由控制要施加的電漿並調節階梯結構的上下部膜或側部膜的特性來實現。例如，可以在蝕刻期間藉由利用自由基的直線性，來使在垂直於自由基行進方向的方向上的上部膜和下部膜比側部膜更硬，而去除側部膜。相反，藉由增強電漿的強度以增強離子轟擊，可以弱化上部膜和下部膜，而不是側部膜的結合結構，從而在蝕刻期間去除上部膜和下部膜。
此過程可以藉由改變電漿施加條件來完成。例如，在特定電漿功率或電漿密度以下，在垂直於自由基行進方向的薄膜表面上，薄膜緻密化可能占主導。相反，在特定電漿功率或電漿密度以上，在垂直於自由基行進方向的薄膜表面上，薄膜結合結構可能被弱化。
一或多個實施例包括基板處理方法，基板處理方法可藉由在形成於階梯結構上的薄膜的整個厚度範圍內實現均勻的蝕刻選擇性，來改善薄膜的蝕刻選擇性。
另外的態樣將在下面的描述中部分地闡述，並且部分地從描述中將是顯而易見的，或者可以藉由實踐本揭露的所呈現的實施例而獲知。
根據一或多個實施例，一種基板處理方法包括：藉由執行多個迴圈而在基板上形成薄膜，迴圈包括形成至少一層以及在對所述層的第一處理條件下將電漿施加到至少一層；以及在不同於第一處理條件的第二處理條件下將電漿施加到薄膜。
根據基板處理方法的示例，可以設置空氣環境（atmosphere），使得在第一處理條件下施加電漿期間和在第二處理條件下施加電漿期間，電漿離子具有方向性。
根據基板處理方法的另一示例，在第一處理條件下施加電漿期間，薄膜的一部分的結合結構（bonding structure）可以改變，並且在第二處理條件下施加電漿期間，薄膜的一部分的結合結構可以進一步改變。
根據基板處理方法的另一示例，基板處理方法還包括等向性蝕刻操作，其中，在等向性蝕刻操作期間，實現了薄膜的結合結構改變的部分與薄膜的其餘部分之間的蝕刻選擇性。
根據基板處理方法的另一示例，至少一層可以形成在具有上表面、下表面以及在上表面和下表面之間的側表面的階梯結構上，並且薄膜的所述部分對應於形成在上表面和下表面上的薄膜的一部分。
根據基板處理方法的另一示例，上述迴圈的重複導致與階梯結構鄰近的薄膜的第一部分的第一結合結構與遠離階梯結構的薄膜的第二部分的第二結合結構之間的差異，並且在第二處理條件下施加電漿期間，可以減小第一部分的第一結合結構與第二部分的第二結合結構之間的差異。
根據基板處理方法的另一示例，基板處理方法還可以包括等向性蝕刻操作。在等向性蝕刻操作之後，可以去除階梯結構的上表面和下表面上的薄膜，並且可以保留階梯結構的側表面上的薄膜。
根據基板處理方法的另一示例，在第二處理條件下施加電漿期間，可以供應含氫氣體。
根據基板處理方法的另一示例，形成至少一層可以包括：供應第一氣體；吹掃第一氣體；以及供應第二氣體並施加電漿以形成第一層。
根據基板處理方法的另一示例，在供應第二氣體和施加電漿以形成第一層期間，將反應空間中的壓力保持在第一壓力，並且在第一處理條件下施加電漿期間，可以將反應空間中的壓力保持在低於第一壓力的第二壓力。
根據基板處理方法的另一示例，在第一處理條件下施加電漿期間供應的功率大於在供應第二氣體和施加電漿以形成第一層期間供應的功率。
根據基板處理方法的另一示例，可以在與第一處理條件不同的第二處理條件下施加電漿期間供應第一氣體。
根據基板處理方法的另一示例，在第一迴圈期間，可以多次執行供應第一氣體、吹掃第一氣體以及供應第二氣體並施加電漿以形成第二層。
根據基板處理方法的另一示例，在第一迴圈期間，將在第一處理條件下的電漿施加到第一層，使得第一層的一部分的濕式蝕刻速率（WER）可以由於電漿離子的離子轟擊效應而增加。
根據基板處理方法的另一示例，在第一迴圈之後的第二迴圈期間，執行在第一層上形成第二層，其中，形成第二層可以包括：供應第一氣體；吹掃第一氣體；以及供應第二氣體並施加電漿以形成第二層。
根據基板處理方法的另一示例，在第二迴圈期間，將在第一處理條件下的電漿施加到第二層和第二層下方的第一層，使得第一層的一部分和第二層的一部分的濕式蝕刻速率可以由於電漿離子的離子轟擊效應而增加，其中，第一層的濕式蝕刻速率可以大於第二層的濕式蝕刻速率。
根據基板處理方法的另一示例，將第二處理條件的電漿施加到第一層和第二層，從而可以減小第一層的濕式蝕刻速率和第二層的濕式蝕刻速率之間的差異。
根據一或多個實施例，一種基板處理方法包括：形成第一層；將第一電漿施加到第一層以改變第一層的一部分的特性；在第一層上形成第二層；將第二電漿施加到第一層和第二層，以改變第一層和第二層的相應部分的特性；以及將第三電漿施加到第二層，以減小第一層的所述部分的特性與第二層的所述部分的特性之間的差異。
根據基板處理方法的示例，在施加第一電漿和施加第二電漿期間，可以使用第一處理條件，並且在施加第三電漿期間，可以使用不同於第一處理條件的第二處理條件。
根據一或多個實施例，一種基板處理方法包括：藉由多次執行包括供應第一氣體到基板和供應與第一氣體具有反應性的第二氣體的迴圈，來在基板上形成薄膜，其中，由於迴圈的重複，薄膜與基板鄰近的第一部分的濕式蝕刻速率高於薄膜遠離基板的第二部分的濕式蝕刻速率；以及減小第一部分的濕式蝕刻速率與第二部分的濕式蝕刻速率之間的差異。
現在將詳細參考實施例，其示例在附圖中示出，其中，相似的附圖標記始終表示相似的元件。就這一點而言，本實施例可以具有不同的形式，並且不應被解釋為限於這裡闡述的描述。因此，下面僅藉由參考附圖描述實施例以解釋本說明書的各態樣。如本文所使用的，術語“及/或”包括一或多個相關聯的所列項目的任何和所有組合。當諸如“...中的至少一個”之類的表達在元件列表之前時，修飾整個元件列表而並不是修飾列表的單一元件。
將理解，儘管術語“第一”、“第二”等在本文中可用於描述各種構件、部件、區域、層及/或部分，但是這些構件、部件、區域、層及/或部分不應受這些術語的限制。這些術語不表示任何順序、數量或重要性，而僅用於區分一個部件、區域、層及/或部分與另一部件、區域、層及/或部分。因此，在不脫離實施例的教導的情況下，下面討論的第一構件、部件、區域、層或部分可以被稱為第二構件、部件、區域、層或部分。
在本說明書中，術語“氣體”可以包括蒸發的固體及/或液體，並且可以包括單一氣體或氣體混合物。在本說明書中，藉由噴淋頭引入到反應室中的製程氣體可以包括前驅物氣體和添加氣體。前驅物氣體和添加氣體通常可以作為混合氣體引入，或者可以獨立地引入反應空間。可以將前驅物氣體與諸如惰性氣體的載體氣體一起引入。添加劑氣體可以包括稀釋氣體，諸如反應氣體和惰性氣體。反應氣體和稀釋氣體可以混合或分別引入反應空間。前驅物可包括兩種或更多種前驅物，並且反應氣體可包括兩種或更多種反應氣體。前驅物是被化學吸附到基板上並且通常包含構成介電膜的基質的主要結構的准金屬（metalloid）或金屬元素的氣體，並且用於沉積的反應氣體是當被激發以在基板上固定原子層或單層時，與被化學吸附到基板上的前驅物反應的氣體。術語“化學吸附”可以指化學飽和吸附。除了製程氣體以外的氣體，即不經過噴淋頭而被引入的氣體，可以用於密封反應空間，並且可以包括諸如惰性氣體的密封氣體。在一些實施例中，術語“膜”可以指在垂直於厚度方向的方向上連續延伸，而基本上不具有小孔以覆蓋整個靶標或相關表面的層，或者可以指僅覆蓋靶標或相關表面的層。在一些實施例中，術語“層”可以指具有在表面上形成的任何厚度的膜或非膜結構的結構或同義詞。膜或層可以包括具有某些特性的離散的單個膜或層或多個膜或層，並且相鄰膜或層之間的邊界可以是清晰的或不清晰的，並且可以基於相鄰膜或層的物理、化學及/或一些其他特性、形成過程或順序及/或功能或目的來設置。
在本揭露中，表述“包含Si-N鍵”可以被稱為以Si-N鍵為特徵，其具有主要由Si-N鍵構成的主骨架及/或具有主要由Si-N鍵構成的取代基。氮化矽層可以是包含Si-N鍵的介電層，並且可以包括氮化矽層（SiN）和氧氮化矽層（SiON）。
在本揭露中，表述“相同材料”應解釋為意味著主要成分（構成）相同。例如，當第一層和第二層都是氮化矽層並且由相同的材料形成時，第一層可以選自Si2 N、SiN、Si3 N4 、和Si2 N3 ，並且第二層也可以是選自上述組，但是其特定的膜品質可以不同於第一層的膜品質。
另外，在本揭露中，根據可操作範圍可基於一般作業來確定，任何兩個變數可構成變數的可操作範圍，並且任何指示的範圍可包括或排除端點。另外，任何指示的變數的值都可以指精確值或近似值（無論它們是否被指示為“大約”），可以包括等效項（equivalents），並且可以指平均值、中值（median value）、代表值、多數值等。
在本揭露中，在未指定條件及/或結構的情況下，根據本揭露，依照一般實驗，本領域普通技術人員可以容易地提供這些條件及/或結構。在所有描述的實施例中，出於預期目的，實施例中使用的任何部件可以用其均等部件替換，包括本文明確、必要或本質上描述的部件，並且此外，本揭露可以類似地應用於裝置和方法。
在下文中，將參考附圖描述本揭露的實施例。在附圖中，例如由於製造技術及/或公差導致的圖示形狀的變化是可以預期的。因此，本揭露的實施例不應被解釋為限於在此示出的區域的特定形狀，而可以包括例如由製造過程引起的形狀偏差。
第1圖是根據本發明實施例的基板處理方法的流程圖。
參照第1圖，基板處理方法可以包括形成至少一層的操作S110和在第一處理條件下施加電漿的操作S120。操作S110和S120可以作為一個組迴圈重複多次，並且可以藉由重複在基板上形成薄膜。基板處理方法還可包括在不同於第一處理條件的第二處理條件下施加電漿的操作S150。
在形成至少一層的操作S110期間，可以在階梯結構上形成薄膜。即，可以在具有上表面、下表面以及在上表面和下表面之間的側表面的階梯結構上形成薄膜。階梯結構可以是具有高縱橫比（aspect ratio）的結構，並且縱橫比可以例如大於或等於寬度：高度＝ 1：10。為了在這樣的高縱橫比的階梯結構上形成保形（conformal）薄膜，可以使用原子層沉積（atomic layer deposition，ALD）製程。特別地，可以使用電漿原子層沉積製程（plasma atomic layer deposition process，PEALD）。
在形成至少一層的操作S110期間，可以設置空氣環境以使得電漿離子的平均自由路徑減小並且電漿離子沒有方向性（即，使得電漿離子的隨機運動增加）。這樣的空氣環境可以有助於在具有高縱橫比的階梯結構上形成保形薄膜。為了實現上述空氣環境，可以形成高壓空氣環境（例如10至20托耳（Torr））。在另一實施例中，為了實現上述空氣環境，可以形成低功率空氣環境（例如200瓦（W）至500瓦）。在另一實施例中，為了實現上述空氣環境，可以形成高溫空氣環境。
在形成至少一層的操作S110期間，可以使用電漿形成層。例如，操作S110可以包括供應第一氣體、吹掃第一氣體、以及供應第二氣體和施加電漿以形成第一層。藉由施加電漿，可以激發第二氣體以使其變得具有反應性，並且具有反應性的第二氣體可以與第一氣體反應以形成第一層。
第一氣體可以包括作為源氣體化學吸附在基板上的材料。第二氣體可以包括與第一氣體具有反應性的材料，特別是在電漿空氣環境下與第一氣體具有反應性的材料。在替代實施例中，第二氣體的供應和電漿的施加可以同時執行。在另一實施例中，在供應第二氣體之後，可以執行電漿的施加。
可以執行多次（例如，a個迴圈）形成至少一層的操作S110。更詳細地，可以多次執行包括形成至少一層的操作S110和在第一處理條件下施加電漿的操作S120的組迴圈GC。可以在一個組迴圈GC期間多次執行形成至少一層的操作S110。因此，在一個迴圈期間，可以執行多次包括在形成至少一層的操作S110中的供應第一氣體、吹掃第一氣體、以及供應第二氣體和施加電漿以形成第二層。
在形成至少一層的操作S110之後，執行在第一處理條件下施加電漿的操作S120。在第一處理條件下施加電漿的操作S120可以執行持續特定時間（例如b秒）。藉由在第一處理條件下施加電漿，可以改變至少一層的一部分的結合結構。在第一處理條件下施加電漿的操作S120期間，可以將電漿離子設置為定向的（directional）。另一方面，如上所述，在形成至少一層的操作S110期間，可以將電漿離子設置為不具有方向性。
定向電漿離子可以改變一部分薄膜的結合結構。例如，在具有高縱橫比的階梯結構上形成薄膜的情況下，可以將電漿離子的方向性設定為面對階梯結構的上表面或下表面。在這種情況下，電漿離子可以改變形成在階梯結構的上表面或下表面上的薄膜的結合結構。相反，定向電漿離子可以不影響在階梯結構的側面上形成的薄膜的結合結構。
如上所述，在形成至少一層的操作S110中，可以在供應第二氣體並施加電漿的同時將反應空間中的壓力保持在第一壓力（例如，高壓），以使反應氣體的隨機運動可以增加。相反，在第一處理條件下施加電漿的操作S120中，反應空間中的壓力可以保持在小於第一壓力的第二壓力（例如，低壓）下，使得反應氣體的運動為定向的。
此外，在形成至少一層的操作S110中，可以將在操作S110期間供應的功率維持在第一功率值（例如，低功率值），使得反應氣體受功率的影響較小（即，電漿離子變得沒有方向性）。相反，在第一處理條件下施加電漿的操作S120中，可以將在操作S120期間供應的功率維持在高於第一功率值的第二功率值（例如，高功率值），使得反應氣體受功率的影響更大（即，電漿離子變成定向的）。
形成至少一層的操作S110和在第一處理條件下施加電漿的操作S120可以被定義為一個組迴圈GC，並且可以重複地執行此組迴圈GC。換句話說，在操作S100中，在執行組迴圈GC之前將X值設置為1，並且在操作S140中，在執行包括形成至少一層的操作S110和在第一處理條件下施加電漿的操作S120的組迴圈GC之後，增加X值，並且在操作S130中當X值達到特定值時，終止組迴圈GC並執行後續操作。
作為後續操作，執行在第二處理條件下施加電漿的操作S150。在第二處理條件下施加電漿的操作S150可以執行持續特定時間（例如，y秒）。藉由在第二處理條件下施加電漿，可以進一步改變至少一層的一部分的結合結構。在第二處理條件下施加電漿的操作S150期間，可以將電漿離子設置為定向的。
例如，可以將電漿離子設置為指向至少一層。在這種情況下，由於電漿離子至少朝向此層入射，因此至少一層的結合結構改變的部分將是形成在圖案結構的上表面和下表面上的部分。當電漿的功率高於閾值時，形成在至少一層的上表面和下表面上的部分將被弱化，並且當電漿的功率低於閾值時，形成在至少一層的上表面和下表面上的部分將是緻密的。
在第一處理條件下施加電漿的操作S120和在第二處理條件下施加電漿的操作S150的共同點在於它們改變了薄膜的結合結構。但是，由於第一處理條件和第二處理條件不同，因此藉由第一處理條件改變了結合結構的薄膜的厚度範圍與藉由第二處理條件改變了結合結構的薄膜的厚度範圍不同。
更詳細地，當重複包括形成至少一層的操作S110和在第一處理條件下施加電漿的操作S120的迴圈時，在初始形成的層（即，鄰近階梯結構的薄膜的第一部分）的情況下，由於電漿施加而導致的結合結構的變化可以被累積。同時，在後來形成的層（即，遠離階梯結構的薄膜的第二部分）的情況下，僅執行少量電漿施加（或一次電漿施加），因此結合結構的變化可能相對較小。
為了抵消結合結構中的這種局部差異，可以施加在第二處理條件下的電漿。例如，在第二處理條件下的電漿可被施加，以引起遠離階梯結構的薄膜的第二部分的結合結構的變化，並且不影響鄰近階梯結構的薄膜的第一部分的結合結構。藉由在第二處理條件下施加電漿，可以減小第一部分的結合結構和第二部分的結合結構之間的差異。
在一實施例中，可在第二處理條件下施加電漿的操作S150期間供應含氫氣體。藉由使用含氫氣體進行電漿處理，可以在遠離階梯結構的薄膜的第二部分中形成更多的Si-H鍵。因此，可以在隨後的蝕刻製程中增加相應部分的蝕刻速率。
在另一實施例中，可以在第二處理條件下施加電漿的操作S150期間供應與在形成至少一層的操作S150中供應的氣體相同的氣體。例如，可以在形成至少一層的步驟S110期間執行供應第一氣體（例如，源氣體）、吹掃第一氣體、以及供應第二氣體（例如，反應氣體）和施加電漿以形成第一層。可以在第二處理條件下施加電漿的操作S150期間供應第一氣體（例如，源氣體）。
在這種情況下，可以藉由在第二處理條件下施加電漿，而在形成於階梯結構的上表面和下表面的薄膜的表面上保持離子轟擊效應的同時，在階梯結構的側表面上另外形成薄膜。在弱化薄膜的結合結構的情況下這是特別有利的，因為在階梯結構的側表面上進一步形成薄膜，而在上表面和下表面上形成的薄膜被定向電漿弱化，從而增加蝕刻選擇性。此外，由於在電漿施加期間供應的源氣體，可以減小電漿離子對在側表面上形成的薄膜的離子轟擊作用。
在第二處理條件下施加電漿的操作S150之後，進行在藉由執行多個組迴圈形成的薄膜上進行等向性蝕刻的操作S160。例如，可以執行薄膜的濕式蝕刻。例如，可以藉由將其上沉積有諸如薄膜的半導體裝置的基板浸入液體蝕刻溶液中並藉由化學反應蝕刻表面來執行濕式蝕刻。由於這種濕式蝕刻是等向性蝕刻，因此這樣的等向性蝕刻本身可以不顯著影響形成在階梯結構上的薄膜的選擇性蝕刻。
在等向性蝕刻的操作S160期間，可以實現薄膜的結合結構被改變的部分與薄膜的其餘部分之間的蝕刻選擇性。換句話說，藉由執行在第一處理條件下施加電漿的操作S120和在第二處理條件下施加電漿的操作S150，在階梯結構上的薄膜的一部分（階梯結構的上表面和下表面上的薄膜）的結合結構改變，從而在等向性蝕刻期間可以去除一部分薄膜，而保留其他部分。藉由去除階梯結構上的一部分薄膜，階梯結構的表面可以被暴露。因此，可以藉由隨後的蝕刻製程來實現薄膜的選擇性蝕刻。因此，可以形成在階梯結構的一區域上形成的圖案化薄膜，而無需單獨的額外微影製程。
根據本發明構思的實施例，利用了在第一處理條件下施加電漿的操作S120和在與第一處理條件不同的第二處理條件下施加電漿的操作S150的組合。與僅施加一種處理條件的電漿的情況相比，藉由組合並施加具有不同處理條件的電漿，可以在形成於階梯結構上的薄膜的整個厚度範圍上實現均勻的蝕刻選擇性。
當僅執行在第一處理條件下施加電漿的操作S120時，隨著迴圈的重複，出現多次施加電漿的區域。因此，藉由多次施加電漿，在薄膜的深部分中蝕刻選擇性增加，而在薄膜的表面中蝕刻選擇性相對降低。在表面處的蝕刻選擇性低的情況下，由於為了形成適當厚度的側部膜而需要將薄膜的厚度沉積為比目標厚度更厚，因此降低了生產率。
當僅執行在第二處理條件下施加電漿的操作S150時，可以藉由離子轟擊效應及/或反應性物質（例如，氫離子）滲透到薄膜中來實現高蝕刻選擇性。然而，藉由轟擊效應和反應性物質的滲透增加了基板中缺陷的可能性。為了防止這種情況，當降低電漿功率或降低反應性物質的穿透力時，出現如下問題：在薄膜的深部分（即，與堆疊結構及/或基板鄰近的部分）處的蝕刻選擇性降低。結果，為了形成適當厚度的側部膜，需要將薄膜的厚度沉積為比目標厚度更厚，從而降低了生產率。
藉由執行在第一處理條件下施加電漿的操作S120和在與第一處理條件不同的第二處理條件下施加電漿的操作S150的組合，可以彌補它們各自的缺點。換句話說，藉由組合，與僅執行單獨的電漿施加處理的情況相比，可以實現明顯改善的效果。
電漿離子導致的薄膜的一部分的結合結構的變化可以是結合結構的弱化，或者可以是結合結構的緻密化。在下文中，將在弱化結合結構的前提下更詳細地描述實施例。
可以設置空氣環境，使得在第一處理條件下施加電漿的操作S120和在第二處理條件下施加電漿的操作S150期間，電漿離子具有方向性。藉由定向的電漿離子的離子轟擊作用可以弱化一部分薄膜的結合結構。
更詳細地，電漿離子可具有垂直於階梯結構的上表面和下表面的方向。因此，薄膜的上表面和下表面的結合結構可以被弱化。結果，藉由後續的等向性蝕刻的操作S160，可以去除階梯結構的上表面和下表面上的薄膜，並且可以保留階梯結構的側表面上的薄膜。
在第一組迴圈期間，可以執行形成至少一層的操作S110以具有多個子迴圈。在各個子迴圈期間，可以執行供應第一氣體、吹掃第一氣體、以及供應第二氣體和施加電漿以形成第一層。
在第一組迴圈期間和子迴圈之後，可以在第一處理條件下施加電漿持續特定時間。藉由在第一處理條件將電漿施加到第一層，由於電漿離子的離子轟擊效應，第一層的一部分的濕式蝕刻速率可以增加。
這將結束第一組迴圈並開始第二組迴圈。在第二組迴圈期間，可以執行形成至少一層的操作S110以具有多個子迴圈。在第二組迴圈期間形成的第二層將形成在第一層上。在第二組迴圈的各個子迴圈中，可以執行供應第一氣體、吹掃第一氣體、以及供應第二氣體和施加電漿以形成第二層。
在第二組迴圈期間以及在用於形成第二層的子迴圈之後，可以在第一處理條件下施加電漿持續特定時間。藉由在第一處理條件下將電漿施加到第二層，由於電漿離子的離子轟擊效應，第二層的一部分的濕式蝕刻速率可以增加。同時，施加的電漿不僅可以影響第二層，而且可以影響第二層下方的第一層。因此，第一層的一部分的濕式蝕刻速率可以進一步增加，因此，第一層的濕式蝕刻速率可以大於第二層的濕式蝕刻速率。
在第一組迴圈和第二組迴圈之後，可以朝向第一層和第二層施加在第二處理條件下的電漿。如上所述，第二處理條件可以不同於第一處理條件。特別地，第二處理條件可以是弱化上部的第二層但不顯著影響下部的第一層的處理條件。例如，第二處理條件可以產生具有低滲透性的反應性物質，並且反應性物質可以僅弱化上面的第二層並且不顯著影響下面的第一層。結果，藉由施加第二處理的電漿，可以減小第一層的濕式蝕刻速率和第二層的濕式蝕刻速率之間的差異。
雖然在本揭露中描述了在第二組迴圈之後施加第二處理條件下的電漿，但是可以在第二組迴圈和第二處理條件下施加電漿之間執行附加的組迴圈。例如，可以在第二組迴圈之後執行第三組迴圈。在第三組迴圈期間，可以執行形成至少一層的操作S110，以具有多個子迴圈。在第三組迴圈期間形成的第三層將形成在第一層和第二層上。
隨後，將在第一處理條件下的電漿施加到第三層，並且由於電漿離子的離子轟擊效應，部分（階梯結構的上表面和下表面上的部分）的濕式蝕刻速率可以增加（請參見第6圖）。隨著迴圈的重複，與基板鄰近的薄膜的第一部分（例如，第一層）將具有比遠離基板的薄膜的第二部分（例如，第二層）更高的濕式蝕刻速率。
為了減小濕式蝕刻速率的差異的目的，在組迴圈（group-cycle）之後進行的第二處理條件下的電漿施加被執行。換句話說，藉由重複組迴圈，重複施加第一處理條件下的電漿以增加薄膜深部分的蝕刻選擇性，而降低薄膜表面的蝕刻選擇性。因此，施加在第二處理條件下的電漿以解決此問題。藉由在第二處理條件下施加電漿，可以增加薄膜表面的蝕刻選擇性，並且因此可以實現均勻的蝕刻選擇性，而與薄膜的厚度（或深度）無關。
第2圖是根據實施例的基板處理方法的視圖。根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出實施例的重複描述。
根據本發明構思的實施例，可以提出基板處理方法以增加沉積在階梯結構的上部和下部上的膜的濕式蝕刻速率，並使濕式蝕刻速率隨時間恆定。例如，可以進行在階梯結構上均勻地沉積硬且均勻的薄膜的第一子步驟，進行電漿處理以增加沉積在階梯結構的側部、上部和下部的薄膜的蝕刻選擇性的第二子步驟，以及使用含氫氣體（例如H2 ）進行電漿處理的第三子步驟。
參照第2圖，在第一子步驟（步驟1）期間，將硬且均勻的氮化矽（SiN）膜均勻地沉積在階梯結構上。例如，可以藉由電漿原子層沉積來沉積氮化矽膜。可以重複第一子步驟（步驟1）多次，並且可以形成具有特定厚度的氮化矽膜。在第二子步驟（步驟2）期間，執行電漿處理b秒（seconds，sec）。將第一子步驟和第二子步驟組成一個組迴圈，並根據所需厚度將重複沉積膜多次（x個迴圈）。在第一子步驟（步驟1）中，施加高處理壓力和低電漿功率以弱化電漿反應性物質的方向性（直線性），並在階梯結構中均勻沉積硬而均勻的氮化矽膜。在第二子步驟（步驟2）中，藉由提供低處理壓力和高電漿功率以提高電漿反應性物質的方向性（直線性），來增加沉積在階梯結構的側部、上部和下部的薄膜的蝕刻選擇性。
第三子步驟（步驟3）是使用含氫氣體的電漿處理步驟，其保持y秒（秒）。維持低壓力和高電漿功率，使得由含氫氣體產生的氫離子（H ions）容易滲透到薄膜中。氫離子可與SiN形成弱鍵或弱化Si-N結合結構。藉由氫離子弱化結合結構可以使在直接進行電漿處理的表面處的效果最大化。在此，保持低的H2 流量以防止氫離子堆積（即，防止在深部分中的薄膜的弱化）。例如，在第三子步驟（步驟3）中，可以在100單位時間標準毫升數（sccm）以下的條件下執行H2 流量。第三子步驟（步驟3）是將沉積膜的表面處的蝕刻選擇性調整為與沉積膜的深部分處的蝕刻選擇性相似的步驟。
在替代實施例中，在第三子步驟（步驟3）的電漿處理中，除了含氫氣體之外，還可以使用易於滲透到薄膜中的其他氣體。可以使用諸如氦氣（He）到氬氣（Ar）的氣體。然後執行濕式蝕刻以在側壁上保留氮化矽膜，並去除在上壁和下壁上的氮化矽膜。
第3圖是根據實施例的基板處理方法的視圖。第4圖是在其中進行基板處理方法的基板處理裝置的圖；根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出實施例的重複描述。
參照第4圖，基板處理裝置可以包括至少一反應器。連接到射頻（RF）發生器的上電極（例如，噴淋頭）和與上電極相對設置的下電極可以設置在反應器中。可以將基板裝載在諸如加熱塊的下電極上，並且可以在基板上執行電漿製程。在一些實施例中，反應器可以是直接電漿反應器。
使用基板處理裝置在基板上形成的層可以是氮化矽層。電漿原子層沉積（PEALD）製程可以用於形成氮化矽層。作為矽（Si）源，可以使用二氯矽烷（SiH2 Cl2 ）、氨基矽烷或碘矽烷的前驅物。作為氮氣源，可以使用氮氣。氮氣在被電漿啟動時會與基板上的物理吸附矽源反應，但在未被電漿啟動時不會與矽源反應，可以用作吹掃氣體。
參照第3圖，組迴圈包括第一子步驟（步驟1）和第二子步驟（步驟2）兩個子步驟，並且每個子步驟可以分別a個迴圈和b個迴圈重複。這些子步驟可以包括在組迴圈中，此組迴圈可以被重複。第一子步驟（步驟1）是在圖案結構上均勻地沉積氮化矽膜的步驟，第二子步驟（步驟2）是電漿處理步驟。
在第二子步驟（步驟2）期間，可以弱化在與自由基的行進方向垂直的方向上沉積在圖案結構的上表面上的氮化矽膜的結合結構。因此，在第二子步驟（步驟2）中，為了增強電漿離子轟擊效果，與第一子步驟（步驟1）相比，可以設置具有較低處理壓力和較高電漿功率的空氣環境。組迴圈後，在100：1稀釋的氟化氫（diluted hydro fluoride，DHF）溶液中進行基板上的濕式蝕刻，結果去除了沉積在圖案結構上表面上的氮化矽膜，並保留了沉積在圖案側表面上的氮化矽膜。
同時，在濕式蝕刻期間，不僅沉積在階梯結構的上表面上的氮化矽膜，而且沉積在階梯結構的側表面上的氮化矽膜被同時蝕刻。然而，上表面上的氮化矽膜的蝕刻速率高，結果，保留在側表面上的氮化矽膜。即，為了實現期望厚度的側壁上的氮化矽膜，當實際沉積氮化矽膜時，需要形成更厚的氮化矽膜。換句話說，當圖案結構的上表面上的氮化矽膜的蝕刻速率較快時，即使在沉積期間形成厚度較小的氮化矽膜，也可以以相同的厚度實現側壁上的氮化矽膜。這將節省處理時間並加快每小時的基板處理速度。第5圖示出了這樣的過程，其中第5圖（a）示出了在階梯結構上形成的氮化矽膜，第5圖（b）示出了在濕式蝕刻之後保留的在階梯結構的側壁上的氮化矽膜。
參照第5圖（a），將氮化矽膜以均勻的厚度沉積在圖案結構上（第5A圖中的上部膜d ＝側部膜c）。由於藉由第3圖的第二子步驟（步驟2）破壞了上氮化矽膜的結合結構，因此在濕式蝕刻期間上氮化矽膜d比側氮化矽膜c被更快地蝕刻。側氮化矽膜上的厚度也被去除了一定程度，但是側氮化矽膜的蝕刻速率比上氮化矽膜的蝕刻速率慢。因此，在濕式蝕刻之後僅保留側氮化矽膜（第5圖（b）中的a）（參見第5圖（b））。即，為了實現期望厚度的側部膜a，需要考慮上部膜d的蝕刻速率來形成附加膜b。
換句話說，上部膜d的蝕刻速率Ed和側部膜c的蝕刻速率Ec決定了選擇性，並且上表面上的蝕刻速率Ed越快，選擇性就越好。如第5圖所示，考慮到上部膜d和側部膜c的蝕刻速率的差異，沉積比所需厚度的側部膜a厚的膜（a+b）。
第6圖示出了根據第3圖的實施例的基板處理方法。參照第6圖，根據原子層沉積方法順序地形成第一氮化矽（SiN）層a、第二氮化矽層b和第三氮化矽層c。在一個迴圈期間對每一層進行氮電漿處理（步驟2）。為了便於理解，在本實施例中，示出了執行三個組迴圈GC1、GC2和GC3（x＝3），並且對於每一層僅執行一次氮電漿處理（步驟2）（b=1）。
在第6圖中，對每個組迴圈進行的氮電漿處理用星號表示。第一標記GC1顯示在沉積第一層a的組迴圈期間施加的氮自由基，第二標記GC2顯示在沉積第二層b的組迴圈期間施加的氮自由基，第三標記GC3顯示在沉積第三層c的組迴圈期間施加的氮自由基。
例如，由於藉由施加高於臨界電漿功率的電漿功率來執行氮電漿處理，所以氮自由基破壞了沉積在圖案的上表面上的氮化矽層的結合結構。儘管在上述實驗中施加氮電漿，但是藉由施加具有大而重元素的氬電漿，可以更容易地破壞膜的結合結構。
如第6圖所示，應該注意的是，當沉積每個膜時，在第二子步驟（步驟2）（其為電漿處理步驟）中施加的電漿也影響下層膜。即，在形成每個層時，在組迴圈中的第二子步驟（步驟2）中，氮電漿處理僅進行一個迴圈（b=1），但是下層進一步經受了電漿處理。換句話說，當依次沉積第一層a、第二層b和第三層c時，與圖案結構鄰近的第一層a經受了三次電漿處理，第一層a上的第二層b經受了兩次電漿處理，遠離圖案結構的第三層c經受了一次電漿處理。這意味著整個塊狀膜（a+b+c）的蝕刻特性不均勻，並且濕式蝕刻速率朝著薄膜的下部更高（Ea＜Eb＜Ec）。
第7圖示出了氮化矽薄膜中的濕式蝕刻速率的變化，氮化矽薄膜是根據第6圖的塊狀膜（bulk film）。橫軸表示蝕刻時間的變化，縱軸表示根據蝕刻時間的蝕刻速率的變化。橫軸和縱軸之間的關係對應於在膜內部從塊狀膜的表面到內部的蝕刻速率的變化。如曲線圖所示，從氮化矽薄膜的表面到深部分，蝕刻速率不均勻。即，可以看出，在施加有較少電漿的氮化矽薄膜的表面部分，濕式蝕刻速率較小，而在藉由重複組迴圈而施加有大量電漿的氮化矽薄膜的深部分（deep portion），濕式蝕刻速率較大。
當塊狀膜的濕式蝕刻特性不均勻時，上表面和側表面之間的選擇性降低。例如，當在沉積製程之後的濕式蝕刻製程的初始階段上表面上的薄膜的蝕刻速率較小時，側表面上的薄膜被蝕刻的量與上表面上的薄膜被蝕刻的量一樣多。相反，當在沉積製程之後的後期濕式蝕刻製程中薄膜的深部分的蝕刻速率較小時，側表面上的薄膜被蝕刻的量與薄膜的深部分被蝕刻的量一樣多。結果，如第8圖所示，當蝕刻圖案結構的上部上的薄膜時，僅具有小於或等於期望厚度a的厚度e的薄膜保留在側表面上，並且結果，降低了上薄膜和側薄膜之間的選擇性。
因此，考慮到此問題，需要在薄膜形成操作中將薄膜沉積為具有相對較厚的厚度。這意味著增加的源和氣體消耗會增加裝置的擁有成本（cost of ownership，COO），並降低每單位時間的基板產量（throughput）。
第9圖是根據實施例的基板處理方法的視圖。根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出實施例的重複描述。
參照第9圖，揭露了一種基板處理方法，其能夠藉由使塊狀膜的蝕刻速率在其整個厚度上均勻而改善塊狀膜的選擇性。可以在由上電極和下電極組成的直接電漿沉積裝置中執行此基板處理方法，如第4圖所示。
在第9圖所示的實施例中，與第3圖的實施例相比，增加了用於執行電漿後處理的第三子步驟（步驟3）。首先，將兩個子步驟（步驟1和步驟2）重複幾次。即，第一子步驟（步驟1）重複a個迴圈，第二子步驟（步驟2）重複b個迴圈。然後，執行組迴圈，以便將此重複（repetition）重複幾次（x個迴圈重複）。在完成組步驟之後，執行用於後電漿處理的第三子步驟（步驟3）。後電漿處理可以重複幾次（例如，y個迴圈）。每個步驟將在下面更詳細地描述。
1、第一子步驟（步驟1）：保形沉積。
作為第一子步驟，此步驟是在圖案上沉積氮化矽膜的步驟。由於沉積了均勻厚度的氮化矽膜，因此沉積在圖案的上部和側部上的氮化矽膜的厚度相同。鹵化物系列（例如二氯矽烷（dichlorosilane，DCS））或氨基矽烷或碘矽烷系列的源氣體可以用作矽源，而氮氣可以用作氮源。當用電漿活化時，氮氣與矽源反應而成為膜的成分，但是當未用電漿活化時，氮氣可以用作吹掃氣體而不與矽源反應。
在第一子步驟期間，將氮化矽膜均勻地施加在圖案結構上，同時藉由電漿原子層沉積方法交替地供應源氣體、反應器氣體和電漿並重複幾次（a個迴圈）。減弱電漿功率以允許將自由基提供給到圖案的內部。電漿功率從200瓦到900瓦，較佳為500瓦。
另外，藉由增加處理壓力以弱化自由基的直線性（straightness），從而允許比圖案底表面提供更多的自由基到圖案側表面，從而促進在側部上形成氮化矽膜。在此步驟中，維持約10托耳至約20托耳的處理壓力。
2、第二子步驟（步驟2）：迴圈電漿處理。
作為第二子步驟，此步驟是對沉積在圖案上的氮化矽膜執行氮電漿處理的步驟。特別地，此步驟是為了增加沉積在上表面和側表面上的膜之間的蝕刻選擇性。如上所述，施加高於臨界電漿功率的電漿功率，以沿垂直於自由基行進方向的方向，來破壞圖案結構的上表面上的膜的結合結構，從而在上部上的薄膜的蝕刻速率高於在側部上的薄膜的蝕刻速率。
在本揭露中，儘管使用與膜的成分相同的氮氣，但是可以使用較重的元素氬氣氣體以更容易地破壞膜的結合結構。在此步驟中，以比第一子步驟（步驟1）中高的約700瓦特至約1000瓦特，較佳地約700瓦特的電漿功率執行電漿處理，以增強自由基直線性和離子轟擊效果。
另外，為了加強在上表面和下表面而不是圖案側面的離子轟擊，將處理壓力設置為低於第一子步驟（步驟1）的壓力。在本揭露中，電漿處理在約1托耳至約5托耳，較佳約3托耳的處理壓力下進行。此步驟也重複幾次（b個迴圈）。另外，將第一子步驟和第二子步驟組合在一起的組步驟重複幾次（x個迴圈）。
3、第三子步驟（步驟3）：後電漿處理。
此步驟是為了解決氮化矽薄膜中濕式蝕刻特性不均勻的問題。在此步驟中，添加氫氣以藉由射頻功率活化氮氣和氫氣的混合氣體。為了促進自由基滲透到圖案的上表面和下表面上的膜中，處理壓力低於沉積步驟（步驟1），電漿功率高於沉積步驟（步驟1）。此步驟以比沉積步驟（步驟1）的電漿功率高的700瓦至1000瓦，較佳為700瓦的電漿功率執行，以增強自由基直線性和離子轟擊效果。
另外，將處理壓力設置為低於沉積步驟（步驟1），以增強在上表面和下表面而不是圖案側面上的離子轟擊。在本揭露中，電漿處理在約1托耳至約5托耳，較佳約3托耳的處理壓力下進行。氫自由基與氮化矽薄膜形成弱結合或弱化氮化矽薄膜的結合結構，並且氫自由基對結合結構的弱化效果在直接經受電漿處理的表面上被最大化。因此，膜表面的耐蝕刻性會變弱。
另外，藉由一起供應氮自由基，可增強上表面和下表面上的氮化矽薄膜的離子轟擊以及由此導致的結合結構的弱化。在本揭露中，儘管使用比其他元素更小和更輕的氫，但是也可以使用氦。在另一實施例中，可以僅供應氫氣而不供應氮氣。
下表1顯示了應用於每個步驟的示例性實驗條件。
表1
第一子步驟 （步驟1） 第二子步驟 （步驟2） 第三子步驟 （步驟3）
氣體流量 （單位時間標準毫升數） 矽源 （載體N2 ） 1000 ~ 5000 0. 0.
反應物N2 5000 ~ 20000 1000 ~ 20000 0 ~ 20000
H2 0. 0. 20 ~ 1000
處理時間 （秒）/迴圈 源供給 0.1 ~ 0.7 0. 0.
吹掃 0.5 ~ 1.0 0. 0.
電漿 3.0 ~ 5.0 3 ~ 60 3 ~ 60
吹掃 0.1 ~ 0.3 0 ~ 1.0 0 ~ 1.0
電漿 射頻功率（瓦） 200 ~ 900 700 ~ 1000 700 ~ 1000
頻率 13.56 MHz 100 kHz ~ 13.56 MHz 100 kHz ~ 13.56 MHz
壓力（托耳） 10 ~ 20 1 ~ 5 1 ~ 5
加熱器溫度（℃） 300 ~ 550 300 ~ 550 300 ~ 550
藉由採用上述表1所示的處理條件，可以提高在圖案結構上沉積薄膜時在圖案的上表面和側表面上沉積的膜之間的蝕刻選擇性。另外，藉由利用電漿原子層沉積方法在圖案上沉積均勻膜的過程（第一子步驟（步驟1）），破壞在圖案的上表面上的膜的結合結構的過程（第二子步驟（步驟2）），以及實現均勻蝕刻特性和高蝕刻速率的過程（第三子步驟（步驟3）），與一般技術相比，對於RTS過程可以實現更高的蝕刻選擇性和效率。
第10圖是示出根據本揭露的處理之後的薄膜的蝕刻特性的圖。如第10圖所示，當應用根據本揭露的條件時，即，當執行第一至第三子步驟（步驟1+步驟2+步驟3）時，濕式蝕刻速率與時間無關而恆定。即，不管氮化矽薄膜中的位置如何，都可以確保恆定的濕式蝕刻速率。
同時，在第一子步驟和第三子步驟（步驟1+步驟3）的實施例的情況下，可以看出，儘管在第三子步驟期間供應的氫自由基（H2 後電漿處理）在破壞薄膜表面的結合結構方面是有效的，但是薄膜的深部分的結合結構不改變，使得濕式蝕刻速率隨時間降低。
在第一和第二子步驟（步驟1+步驟2）的實施例的情況下，可以看出，儘管在第二子步驟期間供應的氮自由基（N2 迴圈電漿處理）在破壞薄膜的深部分的結合結構方面是有效的，但是薄膜表面的結合結構不會改變，使得在蝕刻開始時濕式蝕刻速率較低，這降低了蝕刻選擇性。
因此，根據本發明構思的實施例，藉由結合由氮自由基引起的離子轟擊效應（N2 迴圈電漿處理）以及由氫自由基引起的薄膜表面（後電漿處理）的耐蝕刻性的弱化，可以藉由進一步弱化在上薄膜的整個厚度上的耐蝕刻性，可以進一步改善蝕刻速率。
表2
N2 迴圈電漿處理 N2 迴圈電漿處理+後電漿處理
底部/側部 蝕刻選擇性 6.3. 21.5.
表2示出了在第10圖的實施例中在80秒的濕式蝕刻時間內氮化矽薄膜的蝕刻選擇性的結果。蝕刻在100：1稀釋的氟化氫（DHF）溶液中進行。根據上面的第10圖和表2，與使用氮自由基的迴圈電漿處理（N2 迴圈電漿處理）的結果6.3相比，根據本揭露的結果增加到21.5，從而將選擇性提高了3.4倍或更多。即，除了使用氮自由基的迴圈電漿處理（N2 迴圈電漿處理）以外，還藉由使用氫混合氣體（後電漿處理（Post PT））另外進行電漿處理（後電漿處理），圖案結構上的膜表面的耐蝕刻性被弱化，並且然後可以以均勻且高的蝕刻速率蝕刻上表面膜。即，可以在圖案結構的側面上留下更厚的膜，從而可以實現有效的處理性能。
第11圖示意性地示出了上表2的結果。可以看出，藉由執行根據本揭露的第一至第三子步驟（步驟1+步驟2+步驟3），蝕刻選擇性大大提高（參見第11B圖）。在僅執行第一子步驟和第二子步驟的情況下，側表面膜保留在期望厚度以下，而整個上表面膜被蝕刻（參見第11A圖）。然而，當執行第一至第三子步驟（步驟1+步驟2+步驟3）時，保留了期望厚度的膜。
第12圖是根據實施例的基板處理方法的視圖。根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出實施例的重複描述。
參照第12圖，可以在第三子步驟（步驟3）期間供應源氣體。在此步驟中，藉由供應源氣體來進一步沉積氮化矽薄膜。然而，由於在第三子步驟期間供應了高電漿功率，所以離子轟擊效應變得佔優勢，並且在上表面上新沉積的氮化矽薄膜的密度被弱化。同時，在側表面上新沉積的氮化矽薄膜具有相對弱的離子轟擊效應和相對較高的密度。
另外，由於在第三子步驟期間形成低壓空氣環境，所以除了上表面之外，離子轟擊效應還施加到圖案結構的底表面。即，由於在頂表面和底表面上新沉積的氮化矽薄膜的密度被弱化，並且在側表面上的氮化矽薄膜的密度相對地增加，因此可以在隨後的等向性蝕刻操作（例如，濕式蝕刻操作）中提高蝕刻選擇性。
第13圖是根據實施例的基板處理方法的視圖。根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出實施例的重複描述。
參考第13圖，執行形成第一層的操作S310。第一層可以形成為在圖案結構上具有均勻的厚度。第一層可以包括多個層，並且可以藉由重複執行原子層沉積製程的迴圈來形成多個層。例如，第一層可以是絕緣層。
此後，執行改變第一層的一部分的特性的操作S320。例如，可以藉由在第一處理條件下施加定向能量來改變第一層的一部分的結合結構。更詳細地，可以在與形成在圖案結構的上表面和下表面上的第一層基本垂直的方向上施加第一處理條件的第一電漿，並且由於第一電漿，可以改變第一層的形成在圖案結構的上表面和下表面上的部分的結合結構。
此後，執行在第一層上形成第二層的操作S330。在示例中，可以在第一層和第二層之間插入至少一層。第二層可以形成為在第一層上具有均勻的厚度。第二層可以包括多個層，並且可以藉由重複執行原子層沉積製程的迴圈來形成多個層。例如，第二層可以由與第一層相同的材料形成。
此後，執行改變第一層和第二層的部分的特性的操作S340。例如，可以藉由在第一處理條件下施加定向能量來改變第一層和第二層的部分的結合結構。更詳細地，可以在與形成在圖案結構的上表面和下表面上的第二層基本垂直的方向上施加第一處理條件的第二電漿，並且由於第二電漿，可以改變第一層的形成在圖案結構的上表面和下表面上的部分以及第二層的形成在圖案結構的上表面和下表面上的部分的結合結構。
此後，執行減小第一層的部分的特性與第二層的部分的特性之間的差異的操作S350。當重複上述特性改變操作時，下層重複接收能量，導致上層和下層之間的特性差異。例如，下部第一層的一部分的結合結構的改變程度可以大於上部第二層的一部分的結合結構的改變程度。因此，可執行附加操作S350以減小第一層的一部分的特性和第二層的一部分的特性之間的差異。
作為附加操作S350的示例，可以在與形成在圖案結構的上表面和下表面上的第二層基本上垂直的方向上施加能量（例如，第三電漿），並且此能量可以進一步改變第二層的形成在圖案結構的上表面和下表面上的部分的結合結構。更詳細地，可以藉由在第二處理條件下施加定向能量來改變第二層的一部分的結合結構。
第二處理條件不同於在上述特性改變操作中使用的第一處理條件，並且特別地，可以將第二處理條件設置為僅影響第二層的結合結構而不影響第一層的結合結構。即，可以在第一電漿的施加和第二電漿的施加期間使用第一處理條件，並且可以在第三電漿的施加期間使用與第一處理條件不同的第二處理條件。
藉由使用第二處理條件施加第三電漿，可以僅改變上部第二層的結合結構，而不改變下部第一層的結合結構。因此，可以減小下部第一層的一部分的結合結構的改變程度與上部第二層的一部分的結合結構的改變程度之間的差異。
第14圖是根據實施例的基板處理方法的視圖。根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出實施例的重複描述。
參照第14圖，執行重複迴圈以形成薄膜的操作S510。薄膜可以包括例如氮化物膜，具體地，氮化矽膜。迴圈可包括將第一氣體（例如，源氣體）供應到基板上以及供應與第一氣體具有反應性的第二氣體（例如，反應氣體）。
在重複迴圈期間，可以施加能量。由於能量的重複施加，與基板鄰近的薄膜的第一部分的濕式蝕刻速率可以高於遠離基板的薄膜的第二部分的濕式蝕刻速率。即，在與基板鄰近的薄膜中，在薄膜形成期間反復施加能量，從而提高了濕式蝕刻速率。然而，遠離基板的薄膜可以在薄膜形成的後半部分中僅被啟動有限次數，因此濕式蝕刻速率不會增加。
因此，可以執行抵消這種濕式蝕刻速率差異的附加操作S520。即，可以進一步執行減小第一部分的濕式蝕刻速率與第二部分的濕式蝕刻速率之間的差異的操作S520。例如，藉由設置處理條件使得可以將能量施加到與薄膜的暴露表面鄰近的部分，可以增加與薄膜的暴露表面鄰近的部分（即，第二部分）的濕式蝕刻速率。結果，可以減少由迴圈重複導致的濕式蝕刻速率因薄膜的位置而引起的變化，並且在隨後的濕式蝕刻操作S530期間，可以在薄膜的整個厚度範圍上實現均勻的濕式蝕刻速率。
第15圖示出了根據上述基板處理方法的薄膜蝕刻速率的在階梯狀結構上的氮化矽薄膜形狀。第15圖（a）示出了濕式蝕刻狀態之前的薄膜的形狀。一定厚度的薄膜均勻地沉積在階梯結構上。
第15圖（b）示出了使用第一子步驟和第二子步驟沉積和濕式蝕刻薄膜的示例。由於在濕式蝕刻開始時階梯結構的上部和下部的蝕刻速率較低，因此需要增加過蝕刻速率以去除階梯結構的上部膜和下部膜，從而階梯結構的側面上的膜變得更薄。因此，當需要一定厚度的側部膜時，需要增加膜的沉積厚度並且降低了生產率。
第15圖（b）示出了使用第一子步驟和第三子步驟沉積和濕式蝕刻薄膜的示例。蝕刻速率僅在濕式蝕刻開始時高，並且隨著蝕刻的進行，蝕刻速率迅速降低並收斂至特定值。因此，僅當側部膜的厚度薄時才可能進行圖案化處理，並且當側部膜的厚度厚時，薄膜保留在階梯結構的上部和下部。
第15圖（d）示出根據本發明構思的實施例的使用第一子步驟、第二子步驟和第三子步驟沉積和濕式蝕刻薄膜的示例。由於蝕刻速率隨時間是恆定的並且高，因此可以在短時間內蝕刻階梯狀結構的上部膜和下部膜以減少側部膜損失。另外，由於在濕式蝕刻之後保留的側部膜的厚度變大，因此可以擴展可以應用製程的應用。
第16圖是圖示根據實施例的基板處理方法的圖。根據實施例的基板處理方法可以是根據上述實施例的基板處理方法的變型。在下文中，這裡將不給出對實施例的重複描述。
參照第16圖，基板處理方法可包括形成至少一層（S110）、在第一處理條件下施加電漿（S120）、在與第一處理條件不同的第二處理條件下施加電漿（S150）以及在第二處理條件下吹掃電漿（S155），隨後進行等向性蝕刻操作（S160）。這裡所說的電漿吹掃是指吹掃電漿產物，如電漿產生的離子或自由基。電漿吹掃操作（S155）可以對應於第9圖的步驟t8。
藉由在第二種處理條件下執行電漿吹掃操作（S155），可以提高在圖案結構上形成的薄膜的蝕刻選擇性。更詳細地，實施施加電漿的操作（S150）以改變圖案結構上薄膜的一部分的結合結構，並且啟動保持在圖案結構之間的離子或自由基。藉由執行電漿吹掃的操作（S155），可以去除圖案結構之間殘留的電漿產物。
在一些實施例中，在第二種處理條件下，可在施加電漿的過程中提供含氫氣體。在這種情況下，在第二個處理條件下的電漿吹掃操作（S155）期間，可以從反應空間中除去含氫氣體。氫氣削弱了圖案結構上薄膜的結合結構，但也在圖案結構之間提供氫氣，並在一定程度上影響沉積在圖案結構一側的薄膜。這些圖案結構之間殘留的氫氣可能是提高刻蝕選擇性的一個抑制因素。因此，藉由在第二種處理條件下進行電漿吹掃（S155），並藉由去除圖案結構之間殘留的氫，可以藉由最小化氫氣對圖案結構的一側上的薄膜的影響來提高蝕刻選擇性。
在一些實施例中，在第二處理條件（S150）下施加電漿和在第二處理條件（S155）下的電漿吹掃可以在一個迴圈中進行。也就是說，可以多次重複包括操作（S150和S155）的一個迴圈，以形成滿足特定條件的薄膜。
第17圖示出了在第二處理條件下，根據上述電漿吹掃的存在或不存在，在圖案結構的側壁上的薄膜的濕式蝕刻程度（S155）。第17A圖示出不存在電漿吹掃操作的情況，並且第17B圖示出添加了電漿吹掃操作的情況。
參考第17A圖，在圖案結構上形成薄膜，而不進行電漿吹掃。由於在第二處理條件下處理電漿後進行5分鐘的濕式蝕刻而不進行電漿吹掃，去除圖案結構上和下部的薄膜，並且圖案結構側壁上的薄膜厚度從135埃（angstroms）減小到113埃。也就是說，可以看到濕式蝕刻速率達到了每分鐘4.4埃。
另一方面，在第17B圖中添加了電漿吹掃操作的情況下，可以看出濕式蝕刻速率較低。在圖案結構上形成薄膜後，在第二種處理條件下進行電漿處理，然後進行電漿吹掃。經過5分鐘的濕式蝕刻，去除圖案結構上和下部的薄膜，圖案結構側壁上的薄膜厚度從142埃減小到130埃。也就是說，可以看到濕式蝕刻速率達到了每分鐘2.4埃。
因此，藉由吹掃操作去除了圖案結構之間側壁周圍的氫氣，從而將氫氣對側壁的影響降至最低。結果，防止了側壁上薄膜的結合結構的削弱，並且可以實現高刻蝕選擇性的技術效果。
在第二處理條件（S155）下的電漿吹掃過程中，可用氮氣作為吹掃氣體。也就是說，諸如離子和自由基的電漿產物可以藉由向反應空間供應和排出氮氣來吹掃。在一些實施例中，在第二處理條件（S155）下的電漿吹掃期間，可以在沒有單獨吹掃氣體的情況下施加真空吹掃。在另一個實施例中，在第二處理條件（S155）下的電漿吹掃期間，氮氣吹掃氣體和氫氣可以一起供應。藉由將氮氣吹掃氣體和氫氣一起供應，可以降低壓力波動，使製程更穩定地進行。
下表3顯示了在第二種處理條件下，根據是否存在上述電漿清洗，圖案結構各部分的濕式蝕刻速率（S155）
無吹掃操作 （S155） 吹掃操作 （S155）
濕式蝕刻速率 （WER） （埃/分鐘） 上部 73.6 58.9
側部 13.4 3.1
下部 68.7 63.8
在上部/側部的蝕刻選擇性 5.5 19.0
當在上表3中添加吹掃操作時，隨著氫氣從反應空間中移除，蝕刻速率總體上降低，但是可以看出，與沒有吹掃操作的情況相比，圖案結構的側壁上的膜與上表面上的膜之間的蝕刻選擇性顯著提高。
如上所述，根據本發明，藉由在氫電漿處理操作中添加吹掃操作和去除圖案結構之間側壁附近殘留的氫氣，存在可提高圖案結構上表面和側表面之間蝕刻選擇性的技術效果。
應當理解，本文描述的實施例應僅在描述性意義上考慮，而不是出於限制的目的。每個實施例中的特徵或態樣的描述通常應被認為可用於其他實施例中的其他類似特徵或態樣。儘管已經參考附圖描述了一或多個實施例，但是本領域普通技術人員將理解，可以在不脫離由隨後的權利要求所限定的本發明的精神和範圍的情況下對形式和細節進行各種改變。
a:側部膜,厚度,第一層,第一氮化矽層 b:附加膜,第二層,第二氮化矽層 c:側部膜,第三層,第三氮化矽層 d:上部膜 e:厚度 Ea:濕式蝕刻速率 Eb:濕式蝕刻速率 Ec:蝕刻速率,濕式蝕刻速率 Ed:蝕刻速率 GC:組迴圈 GC1:組迴圈,第一標記 GC2:組迴圈,第二標記 GC3:組迴圈,第三標記 S100:操作 S110:操作 S120:操作 S130:操作 S140:操作 S150:操作 S155:操作 S160:操作 S310:操作 S320:操作 S330:操作 S340:操作 S350:操作 S510:操作 S520:操作 S530:操作 t8:步驟
根據以下結合附圖的描述，本揭露的特定實施例的上述和其他態樣、特徵和優點將變得更加明顯，其中： 第1圖是根據實施例的基板處理方法的流程圖； 第2圖是根據實施例的基板處理方法的圖； 第3圖是根據實施例的基板處理方法的圖； 第4圖是進行基板處理方法的基板處理裝置的圖； 第5圖是在階梯結構上形成的薄膜和等向性蝕刻後保留的膜的視圖； 第6圖是根據實施例的基板處理方法的圖； 第7圖是示出薄膜的濕式蝕刻速度的變化的圖； 第8圖是等向性蝕刻後在階梯狀結構上形成的薄膜保留的狀態的圖； 第9圖是根據實施例的基板處理方法的圖； 第10圖是示出根據本揭露的處理之後的薄膜的蝕刻特性的圖； 第11圖是根據不同基板處理方法獲得的薄膜的蝕刻選擇性的視圖； 第12圖是根據實施例的基板處理方法的圖； 第13圖是根據實施例的基板處理方法的圖； 第14圖是根據實施例的基板處理方法的圖； 第15圖是在等向性蝕刻之後藉由上述基板處理方法形成的薄膜保留的狀態的圖； 第16圖示出根據本揭露實施例的基板處理方法；以及 第17A圖和第17B圖示出根據本揭露的示例的根據存在或不存在電漿吹掃的在圖案結構的側壁上的薄膜的濕式蝕刻的程度。
GC:組迴圈
S100:操作
S110:操作
S120:操作
S130:操作
S140:操作
S150:操作
S160:操作

Claims (21)

  1. 一種基板處理方法，包括： 藉由施行複數個迴圈而在一基板上形成一薄膜，每個迴圈包括形成至少一層以及在一第一處理條件下將電漿施加到該至少一層；以及 在不同於該第一處理條件的一第二處理條件下將電漿施加到該薄膜。
  2. 如請求項1之基板處理方法， 設置一空氣環境，使得在該第一處理條件下施加電漿和在該第二處理條件下施加電漿期間，電漿離子具有方向性。
  3. 如請求項1之基板處理方法， 其中，在該第一處理條件下施加電漿期間，該薄膜的一部分的一結合結構改變，並且 在該第二處理條件下施加電漿期間，該薄膜的一部分的該結合結構進一步改變。
  4. 如請求項3之基板處理方法， 更包括一等向性蝕刻操作， 其中，在該等向性蝕刻操作期間，實現了該薄膜的該結合結構已改變的部分與該薄膜的其餘部分之間的蝕刻選擇性。
  5. 如請求項3之基板處理方法， 其中，該至少一層形成在具有一上表面、一下表面以及在該上表面和該下表面之間的一側表面的一階梯結構上，以及 該薄膜的該部分對應於形成在該上表面和該下表面上的該薄膜的一部分。
  6. 如請求項5之基板處理方法， 其中，該迴圈的重複導致與該階梯結構鄰近的該薄膜的一第一部分的一第一結合結構與遠離該階梯結構的該薄膜的一第二部分的一第二結合結構之間的一差異，以及 在該第二處理條件下施加電漿期間，減小了該第一部分的該第一結合結構與該第二部分的該第二結合結構之間的差異。
  7. 如請求項5之基板處理方法， 更包括一等向性蝕刻操作， 其中，在該等向性蝕刻操作之後，去除了該階梯結構的該上表面和該下表面上的薄膜，並且保留該階梯結構的該側表面上的一薄膜。
  8. 如請求項1之基板處理方法， 在該第二處理條件下施加電漿期間，供應一含氫氣體。
  9. 如請求項1之基板處理方法， 其中，形成該至少一層包括： 供應一第一氣體； 吹掃該第一氣體；以及 供應一第二氣體並施加電漿以形成一第一層。
  10. 如請求項9之基板處理方法， 其中，在供應該第二氣體和施加電漿以形成該第一層期間，將依反應空間中的壓力保持在一第一壓力，並且 在該第一處理條件下施加電漿期間，將該反應空間中的壓力保持在低於該第一壓力的一第二壓力。
  11. 如請求項9之基板處理方法， 其中，在該第一處理條件下施加電漿期間供應的功率大於在供應該第二氣體和施加電漿以形成該第一層期間供應的功率。
  12. 如請求項9之基板處理方法， 其中，在與該第一處理條件不同的該第二處理條件下施加電漿期間供應該第一氣體。
  13. 如請求項9之基板處理方法， 其中，在一第一迴圈期間，多次施行供應該第一氣體、吹掃該第一氣體以及供應該第二氣體並施加電漿以形成該第一層。
  14. 如請求項13之基板處理方法， 其中，在該第一迴圈期間，將在該第一處理條件下的電漿施加到該第一層，使得該第一層的一部分的一濕式蝕刻速率由於電漿離子的一離子轟擊效應而增加。
  15. 如請求項14之基板處理方法， 其中，在施行該第一迴圈之後的一第二迴圈期間，在該第一層上形成一第二層， 其中，形成該第二層包括： 供應一第一氣體； 吹掃該第一氣體；以及 供應一第二氣體並施加電漿以形成該第二層。
  16. 如請求項15之基板處理方法， 其中，在該第二迴圈期間，將在該第一處理條件下的電漿施加到該第二層和該第二層下方的該第一層，使得該第一層的一部分和該第二層的一部分的濕式蝕刻速率由於電漿離子的一離子轟擊效應而增加， 其中，該第一層的濕式蝕刻速率大於該第二層的濕式蝕刻速率。
  17. 如請求項16之基板處理方法， 其中，將在該第二處理條件的電漿向該第一層和該第二層施加，從而減小該第一層的濕式蝕刻速率和該第二層的濕式蝕刻速率之間的一差異。
  18. 一種基板處理方法，包括： 形成一第一層； 將第一電漿施加到該第一層，以改變該第一層的一部分的特性； 在該第一層上形成一第二層； 將第二電漿施加到該第一層和該第二層，以改變該第一層和該第二層的相應部分的特性；以及 將第三電漿施加到該第二層，以減小該第一層的一部分的特性與該第二層的一部分的特性之間的一差異。
  19. 如請求項18之基板處理方法， 其中，在施加該第一電漿和施加該第二電漿期間使用一第一處理條件，以及 在施加該第三電漿期間使用不同於該第一處理條件的一第二處理條件。
  20. 一種基板處理方法，包括： 藉由多次施行包括供應一第一氣體到一基板和供應與該第一氣體具有反應性的一第二氣體的一迴圈，來在該基板上形成一薄膜，其中，由於該迴圈的重複，該薄層的與該基板鄰近的一第一部分的濕式蝕刻速率高於該薄膜的遠離該基板的一第二部分的濕式蝕刻速率；以及 減小該第一部分的濕式蝕刻速率與該第二部分的濕式蝕刻速率之間的一差異。
  21. 如請求項1之基板處理方法，更包括： 在該第二處理條件下吹掃電漿產物。
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