TW202205428A - 用於高深寬比結構之移除方法 - Google Patents

用於高深寬比結構之移除方法 Download PDF

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TW202205428A
TW202205428A TW110134518A TW110134518A TW202205428A TW 202205428 A TW202205428 A TW 202205428A TW 110134518 A TW110134518 A TW 110134518A TW 110134518 A TW110134518 A TW 110134518A TW 202205428 A TW202205428 A TW 202205428A
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徐霖
陳智君
嘉瑩 黃
王安川
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美商應用材料股份有限公司
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Abstract

多種示範性清潔或蝕刻方法可包括，使含氟前驅物流進半導體處理腔室的遠端電漿區域。方法可包括，在該遠端電漿區域內形成電漿，以生成該含氟前驅物的電漿流出物。該等方法亦可包括，使該等電漿流出物流進該半導體處理腔室的處理區域。基板可定位在該處理區域內，且該基板可包括暴露氧化物之區域。方法亦可包括，提供含氫前驅物至該處理區域。該等方法可進一步包括，移除至少一部分的該暴露氧化物，同時將該處理區域內的相對溼度維持在低於約50%。在移除之後，該等方法可包括，將該處理區域內的該相對溼度增加至大於50%或約50%。該等方法可進一步包括，移除額外量的該暴露氧化物。

Description

用於高深寬比結構之移除方法
本技術關於半導體製程與設備。更詳言之，本技術關於清潔或蝕刻高深寬比結構。
積體電路是透過在基板表面上產生錯綜複雜的圖案化材料層的製程而實現。在基板上產生圖案化材料需要用於移除暴露材料的受控方法。化學蝕刻用在各式各樣的目的上，包括將光阻中的圖案轉移到下面的層、使層變薄或使已存在於表面上的特徵之側向尺寸變薄。經常，期望有一種蝕刻製程會蝕刻一種材料蝕刻得比另一種還快，而助於例如圖案轉移製程。此類蝕刻製程被稱作是對第一材料有選擇性。材料、電路、及製程多樣化的結果是，已開發對各式各樣材料有選擇性的蝕刻製程。
蝕刻製程可根據該製程中所用的材料而分為溼式或乾式。溼HF蝕刻優先移除氧化矽勝於其他介電質及材料。然而，溼製程可能在貫穿某些受限溝槽時有所困難，且亦可能有時會使剩餘的材料變形。於基板處理區域內形成的原地電漿中產生的乾蝕刻可貫穿更為受限的溝槽，且呈現出細微剩餘結構較少變形。然而，原地電漿可能在該等電漿放電時產生電弧而損壞基板。
因此，需要可用於產生高品質元件及結構的改善系統及方法。本技術解決了這些及其他需求。
多種示範性的清潔、移除、及蝕刻方法可包括，使含氟前驅物流進半導體處理腔室的遠端電漿區域。該等方法可包括，在該遠端電漿區域內形成電漿，以生成該含氟前驅物的電漿流出物。該等方法亦可包括，使該等電漿流出物流進該半導體處理腔室的處理區域。基板可定位在該處理區域內，且該基板可包括暴露氧化物之區域。該等方法亦可包括，提供含氫前驅物至該處理區域。該等方法可進一步包括，移除至少一部分的該暴露氧化物，同時將該處理區域內的相對溼度維持在低於約50%。在移除之後，該等方法可包括，將該處理區域內的該相對溼度增加至大於50%或約50%。該等方法可進一步包括，移除額外量的該暴露氧化物。
多種示範性方法亦可包括：繼續使該等電漿流出物流進該處理區域，同時增加該處理區域內的相對溼度。可減少該等電漿流出物的流速，同時增加該處理區域內的相對溼度。多個實施例中，可減少該基板之溫度，同時增加該處理區域內的相對溼度。例如，該溫度可減少至少約5°C。多個實施例中，可增加該處理腔室內的壓力，同時增加該處理區域內的相對溼度。例如，該壓力可增加至少約1托耳。一些實施例中，可將該相對溼度增加至超過約65%。在已執行包括移除額外量的暴露氧化物的根據本技術之方法後，該基板中氟濃度可低於5%或約5%。類似地，該基板中氧濃度可低於8%或約8%。一些實施例中，在將該含氫前驅物提供至該處理區域時，該含氫前驅物可繞過該遠端電漿區域。一些實施例中，該處理區域於該等移除操作期間可維持無電漿。此外，示範性方法期間可增量式（incrementally）增加該相對溼度，且可以每增量小於20%或約20%增量式增加將該相對溼度。
本技術亦涵蓋多種清潔方法。該等方法可包括：使含氟前驅物流進半導體處理腔室的遠端電漿區域，同時在該遠端電漿區域內形成電漿，而生成該含氟前驅物的電漿流出物。該等方法可包括，使該等電漿流出物流進該半導體處理腔室的處理區域。該處理區域可容納或含有基板，該基板可包括高深寬比特徵，該特徵具有暴露氧化物之區域。在使該等電漿流出物流進該處理區域的同時，該等方法可包括，提供含氫前驅物至該處理區域。該等方法可進一步包括，移除該暴露氧化物的至少一部分，同時將該處理區域內的相對溼度維持在大於50%或約50%。該等方法可進一步包括：在移除該暴露氧化物的至少一部分之後，增加該含氟前驅物的流速，同時將該處理區域內的該相對溼度維持在大於50%或約50%。該等方法亦可包括，移除額外量的該暴露氧化物。
在多個實施例中，移除額外量的該暴露氧化物可將氧的濃度降低至少約5%。示範性方法中，該含氟前驅物的流速可增加至少約2sccm。多個實施例中，在移除操作前氧化物的暴露區域的厚度可小於2nm或約2nm。此外，在一些實施例中，該高深寬比特徵的臨界尺寸可減少約1%或小於1%。
本技術亦涵蓋多種移除方法。該等方法可包括：使含氟前驅物流進半導體處理腔室的遠端電漿區域，同時在該遠端電漿區域內形成電漿，而生成該含氟前驅物的電漿流出物。該等方法可包括，使該等電漿流出物流進該半導體處理腔室的處理區域。該處理區域可容納基板，該基板可具有一或多個高深寬比特徵，該特徵具有暴露氧化物之區域。在使該等電漿流出物流進該處理區域的同時，該等方法可包括，提供含氫前驅物至該處理區域。該等方法可包括，繼續使該等電漿流出物及該含氫前驅物流進該處理區域達至少約200秒。該等方法亦可包括，移除至少一部分的該暴露氧化物，同時將該處理區域內的相對溼度維持在大於50%或約50%。一些實施例中，該移除操作可將該基板內的氧的表面位階（surface-level）的濃度減少至少約3%。
此技術可提供勝於習知系統及技術的許多優點。例如，該等製程可容許高深寬比特徵得以被蝕刻而不會發展圖案崩塌。此外，該等製程可在限制基板的表面污染程度的同時得以進行材料移除。連同下文的敘述及所附的圖式更詳細地描述這些及其他實施例，以及許多其優點及特徵。
稀釋的酸可用在許多不同的半導體製程上，以清潔基板及從那些基板移除材料。例如，稀釋的氫氟酸可為用於氧化矽的有效蝕刻劑，且可用於從矽表面移除氧化矽。完成蝕刻或清潔操作之後，可從晶圓或基板表面乾燥該酸。使用稀釋的氫氟酸（「DHF」）可稱為「溼」蝕刻，且該稀釋劑通常是水。水具有相對強的表面張力，該表面張力可作用在與水接觸的表面上。
在尺寸上持續縮小的元件圖案化及特徵可包括於基板上蝕刻或形成的細微特徵。舉例而言，許多處理操作可影響或形成基板中的溝槽、孔洞、或其他特徵、或是基板上的材料。深寬比界定為高度對寬度的比，該深寬比在元件中可能會非常高，且可在5、10、20、50、100或更大的量級。這些特徵中的許多特徵可不僅具有高深寬比，而且還具有幾個奈米的尺度上的縮小的尺寸，舉例而言，使得遍及基板的臨界尺寸——經常是這些特徵的寬度或尺寸——可小於10nm、小於5nm、小於3nm、小於2nm、小於1nm、或甚至更小。舉例而言，兩個溝槽之間的任何特定的柱體或壁之寬度可為僅幾個奈米。此材料愈薄，則施加在結構整體上的衝擊應力愈大。此外，構成該結構的材料（若該材料是基板材料、介電質、光阻等）亦可能衝擊材料上所施加之壓力或應力的效應。
當細微、高深寬比特徵受到清潔、蝕刻、或處理時可能有一些問題，因為流體可能呈現表面張力，而該表面張力會遠遠高於該等特徵所能應付的表面張力。在具有多個特徵、層、或材料的設計中，甚至是少量的特徵變形或崩塌都可能引發通過所生產之元件的短路，而導致該元件無法運作。舉例而言，儘管DHF可在低深寬比結構上良好地運作，但是當DHF用作為高深寬比特徵上的蝕刻劑，當蝕刻操作結束且乾燥或移除DHF時，於乾燥期間施加在特徵上的表面張力可能引發圖案崩塌。隨著元件特徵持續縮小，由於溼蝕刻對高深寬比特徵的影響之故，該溼蝕刻可能不再足夠。用於在清潔操作中流體移除的一項有力的技術是藉由以超臨界流體進行乾燥操作。儘管這些技術可提供更乾且較不會圖案崩塌的表面，但製備的量、硬體需求、及所涉及的操作數目可能會減少整體基板處理的效能。
本技術透過執行乾蝕刻製程而克服這些問題，該乾蝕刻製程提供適當的選擇性以相對矽移除氧化矽，同時維持高深寬比結構。該技術利用電漿增強前驅物（該前驅物可包括含氟前驅物）以從矽表面移除氧化矽之暴露區域。透過利用非流體材料，可將基板特徵上的影響減至最少。針對蝕刻的用語「乾」可用於意指液態水可不用於該等操作中，而與溼蝕刻不同，在溼蝕刻中水可用作為諸如DHF的稀釋劑或成分。
儘管其餘的揭露內容會一貫地指明利用所揭露之技術的特定蝕刻製程，但會易於瞭解該等系統及方法同樣可應用至可能會在所述腔室中發生的沉積與清潔製程。因此，不應將該技術視為限制成單獨與蝕刻製程或腔室使用。再者，儘管將示範性腔室描述為提供本技術之基礎，但應瞭解本技術可應用至幾乎任何可容許所述操作的半導體處理腔室。
第1 圖 顯示根據多個實施例的沉積、蝕刻、烘烤、及固化腔室之處理系統100的一個實施例的頂視平面圖。該圖中，一對前開式晶圓盒（FOUP）102供應各種尺寸的基板，該等基板由自動機械臂104接收且放進低壓保持區域106，之後才放進基板處理腔室108a-f之其中一者，該等基板處理腔室108a-f定位在串接區段109a-c中。第二自動機械臂110可用於將基板晶圓從保持區域106輸送到基板處理腔室108a-f且往回輸送。每一基板處理腔室108a-f可裝配成執行許多基板處理操作，包括本文所述之乾蝕刻製程，此外還有循環層沉積（CLD）、原子層沉積（ALD）、化學氣相沉積（CVD）、物理氣相沉積（PVD）、蝕刻、預清潔、去氣、定向、及其他基板製程。
基板處理腔室108a-f可包括一或多個系統部件以沉積、退火、固化、及/或蝕刻基板晶圓上的介電膜。一個組裝型態中，兩對處理腔室（例如108c-d及108e-f）可用於在基板上沉積介電材料，且第三對處理腔室（例如108a-b）可用於蝕刻所沉積的介電質。另一組裝型態中，所有三對腔室（例如108a-f）可組裝成蝕刻基板上的介電膜。所述之製程的任何一者或多者可在與不同實施例中所示的製造系統分開的腔室中執行。將會瞭解，系統100考量用於介電膜的沉積、蝕刻、退火、及固化腔室的額外組裝型態。
第2A 圖 顯示示範性處理腔室系統200的剖面視圖，在處理腔室內有分隔的電漿生成區域。在膜蝕刻（例如，氮化鈦、氮化鉭、鎢、矽、多晶矽、氧化矽、氮化矽、氮氧化矽、碳氧化矽等）期間，處理氣體可穿過氣體入口組件205流進第一電漿區域215。可視情況任選地將遠端電漿系統（RPS）201納入系統中，且該遠端電漿系統201可處理隨後行進穿過氣體入口組件205的第一氣體。該入口組件205可包括兩個或更多個不同的氣體供應通道，其中第二通道（圖中未示）可繞過RPS201（在納入RPS的情況中）。
圖中顯示冷卻板203、面板217、離子抑制件223、噴頭225、及基板支撐件265（上面配置有基板255），且根據多個實施例，可納入上述各者。底座265可具有熱交換通道，熱交換流體流過該熱交換通道而控制基板之溫度，可操作該基板之溫度以在處理操作期間加熱及/或冷卻基板或晶圓。亦可利用嵌入的電阻加熱器元件電阻式加熱底座265的晶圓支撐盤而達成相對高的溫度，該晶圓支撐盤可包括鋁、陶瓷、或上述材料之組合，該溫度諸如從多達100°C或約100°C至超過1100°C或約1100°C。
面板217可為金字塔形、錐形、或具有其他類似結構，該結構為窄的頂部部分擴張成寬的底部部分。另外面板217可如圖所示般平坦且包括用於分配處理氣體的複數個貫穿通道。取決於RPS201之用途，電漿生成氣體及/或電漿激發物種可通過如第2B圖中所示的面板217中的複數個孔洞以更均勻地傳遞至第一電漿區域215中。
示範性組裝型態可包括，使氣體入口組件205開啟至氣體供應區域258，該氣體供應區域258由面板217與第一電漿區域215隔開，使得氣體/物種流過面板217中的孔洞而進入第一電漿區域215。可選擇結構及操作性特徵，以防止電漿從第一電漿區域215明顯回流而回到供應區域258、氣體入口組件205、及流體供應系統210中。面板217（或腔室之導電頂部部分）及噴頭225顯示為具有絕緣環220，該絕緣環220位在特徵之間，而得以相對於噴頭225及/或離子抑制件223施加AC電位至噴頭面板217。該絕緣環220可定位在面板217及噴頭225及/或離子抑制件223之間，而使電容耦合電漿（CCP）得以在第一電漿區域中形成。擋板（圖中未示）可另外位在第一電漿區域215中，或不然則是與氣體入口組件205耦接，而影響透過氣體入口組件205進入區域的流體之流動。
離子抑制件223可包括板件或其他幾何形狀構件，該板件或其他幾何形狀構件於整個結構中界定複數個孔隙（aperture），該等孔隙是組裝成抑制離子式帶電物種遷移出第一電漿區域215同時容許未帶電的中性或自由基物種通過該離子抑制件223進入該抑制件及該噴頭之間的活化氣體遞送區域。多個實施例中，該離子抑制件223可包括穿孔板（perforated plate），該穿孔板具有各種孔隙的組裝型態。這些未帶電的物種可包括高反應性物種，該等高反應性物種是以較不反應性的載氣輸送通過孔隙。如上文所記敘，可減少離子性物種通過該等孔洞的遷移，且在一些例子中該遷移可被完全地抑制。控制離子性物種通過離子抑制件223的量可有利地增加針對帶至與下方晶圓基板接觸的氣體混合物的控制，且轉而可增加氣體混合物的沉積及/或蝕刻特性的控制。例如，氣體混合物之離子濃度的調整可明顯改變其蝕刻選擇性，例如SiNx :SiOx 蝕刻比、Si:SiOx 蝕刻比等。在其中執行沉積的替代性實施例中，亦能夠針對介電材料平移正形對可流動（conformal-to-flowable）類型的沉積的平衡。
離子抑制件223中的複數個孔隙可組裝成控制活化氣體（即離子、自由基、及/或中性物種）通過離子抑制件223。舉例而言，該等孔洞的深寬比（或孔洞的直徑對長度）及/或該等孔洞的幾何形狀可經控制，而使得減少了活化氣體中通過離子抑制件223的離子式帶電物種的流動。離子抑制件223中的孔洞可包括漸縮部分及圓柱狀部分，該漸縮部分面向電漿激發區域215，該圓柱狀部分面向噴頭225。該圓柱狀部分的形狀及尺寸可設計成控制離子物種通過而至噴頭225的流動。也可將可調整的電偏壓施加至離子抑制件223而作為控制通過抑制件的離子物種之流動的額外手段。
離子抑制件223可作用為減少或消除離子式帶電物種從電漿生成區域行進至基板的量。未帶電的中性及自由基物種仍可通過離子抑制件中的開口，而與基板反應。應注意，在多個實施例中，可不完全消除環繞基板的反應區域中的離子式帶電物種。某些例子中，希望離子物種抵達基板，以執行蝕刻及/或沉積製程。這些例子中，該離子抑制件可助於將反應區域中的離子物種的濃度控制在有助製程的層級。
噴頭225結合離子抑制件223可使電漿存在於第一電漿區域215中，以避免在基板處理區域233中直接激發氣體，同時仍使受激發的物種從腔室電漿區域215行進至基板處理區域233中。以此方式，該腔室可組裝成防止電漿接觸受蝕刻的基板255。此舉可有利地保護基板上圖案化的各種複雜的結構及膜，若該結構與膜直接接觸所生成的電漿可能會受到損壞、移位、或不然則是翹曲。此外，當電漿得以接觸基板或抵達基板的位高（substrate level）時，氧化物物種蝕刻的速率可能增加。因此，若材料的暴露區域是氧化物，則此材料可能透過將電漿維持得遠離該基板而進一步受到保護。
該處理系統可進一步包括電源供應器240，該電源供應器240電耦接該處理腔室，以提供電力給面板217、離子抑制件223、噴頭225、及/或底座265，以在第一電漿區域215或處理區域233中生成電漿。取決於執行的製程，該電源供應器可組裝成遞送可調整的量的電力給腔室。此類組裝型態可容許有可調的電漿用於執行的製程中。有別於遠端電漿單元（經常供有開或關的功能性），可調的電漿可設成遞送特定量的電力給電漿區域215。這轉而可容許發展特定的電漿特性，使得前驅物可透過特定方式解離，而增強這些前驅物所產生的蝕刻分佈曲線（etching profile）。
可在噴頭225上方的腔室電漿區域215中或是在噴頭225下方的基板處理區域233中點燃電漿。電漿可存在於腔室電漿區域215中以從例如含氟前驅物或其他前驅物的流入物產生自由基前驅物。可將一般在射頻（RF）範圍的AC電壓施加在處理腔室的導電頂部部分（諸如面板217）及噴頭225及/或離子抑制件223之間，以在操作期間於腔室電漿區域215點燃電漿。RF電源供應器可生成13.56MHz的高RF頻率，但亦可單獨生成其他頻率或結合13.56MHz的頻率生成其他頻率。
第2B 圖 顯示影響通過面板217的處理氣體分佈的特徵的詳細視圖253。如第2A圖與第2B圖中所示，面板217、冷卻板203、及氣體入口組件205交錯而界定氣體供應區域258，處理氣體可從氣體入口205遞送至該氣體供應區域258。該等氣體可填充氣體供應區域258且透過面板217中的孔隙259流至第一電漿區域215。孔隙259可組裝成以實質上單一方向的方式引導流動，使得處理氣體可流進處理區域233，但可部分地或完全地防止在橫越面板217之後回流至氣體供應區域258。
諸如噴頭225之類的用在處理腔室區段200中的氣體分配組件可稱作雙通道噴頭（DCSH），且於第3圖中所描述的實施例中另外詳細提及。雙通道噴頭可供應蝕刻製程，該等蝕刻製程容許在處理區域233外分開蝕刻劑，而提供該等蝕刻劑在被遞送至處理區域中之前彼此之間及與腔室部件之間的交互作用受到限制。
噴頭225可包括上板214及下板216。該等板可彼此耦接，而在這些板之間界定容積218。耦接這些板可為了提供穿過上板及下板的第一流體通道219及穿過下板216的第二流體通道221。所形成的通道可組裝成提供從空間218通過下板216的流體進出（單獨透過第二流體通道221），且第一流體通道219可與該等板及第二流體通道221之間的容積218流體隔離。可穿過氣體分配組件225的側面在流體上進出該容積218。
第3 圖 是根據多個實施例與處理腔室一併使用的噴頭325之底視圖。噴頭325可對應第2A圖中所示的噴頭225。貫穿孔洞365（顯示第一流體通道219之視角）可具有多種形狀及組裝型態，以控制及影響穿過噴頭225的前驅物的流動。小孔洞375（顯示第二流體通道221的視角）可實質上均勻分佈在噴頭表面上方，甚至是在貫穿孔洞365之間，且相較於其他組裝型態可助於在前驅物離開噴頭時提供更為均勻的前驅物混合。
上文論述的腔室可用在執行包括蝕刻方法的示範性方法。轉至第 4 圖 ，第4圖顯示根據本技術的實施例的方法400的示範性操作。在該方法的第一操作之前，可用一或多種方式處理基板，之後再將該基板放置在腔室的處理區域內，可在該處理區域中執行方法400。例如，溝槽、孔洞、或其他特徵可形成在基板中，該基板可包括矽基板。在一些實施例中，孔洞可由反應性離子蝕刻形成，該反應性離子蝕刻可利用氧化物硬遮罩。反應性離子蝕刻可產生深的高深寬比結構，但可能在所形成的結構內留下殘餘物，該殘餘物可能包括碳、氧、或其他材料。可執行灰化操作，然而氧化物殘餘材料仍可能留在所形成的結構中。這些操作的其中一些或全部可在先前描述的腔室或系統工具中執行，或可在相同的系統工具上的不同腔室中執行，該系統工具可包括其中執行方法400之操作的腔室。
方法400可包括，在操作405，將含氟前驅物流進半導體處理腔室的遠端電漿區域中。示範性腔室可為先前描述的腔室200，該腔室200可包括RPS單元201或第一電漿區域215之一者或兩者。這些區域的任意一者或兩者可為用在操作405中的遠端電漿區域。於操作410，電漿可在該遠端電漿區域內生成，而可生成含氟前驅物的電漿流出物。於操作415，該等電漿流出物可流至腔室的處理區域。該等電漿流出物可於處理區域中與基板交互作用，該基板可包括形成穿過半導體基板的溝槽或其他特徵，該半導體基板可包括矽、鍺、或任何其他基板或可理解的元素的組合。
該基板可包括暴露氧區域，該氧可來自一或多個來源。例如，該氧可為已形成溝槽或其他特徵之後留下來的氧硬遮罩。該氧化物亦可為已由基板暴露至空氣而形成的氧化物之層或包括該氧化物之層。例如，當基板暴露至空氣或某些其他氧來源時，氧化物薄層可於基板上形成。在操作420，可將含氫前驅物連同電漿流出物提供至處理區域。在操作425，該等電漿流出物及含氫前驅物可與暴露氧化物交互作用而移除至少一部分的暴露氧化物。移除期間，處理區域內的相對溼度可維持在低於50%或約50%。
已於操作425移除該氧化物的一部分之後，在操作430，處理區域內的相對溼度可增加至大於50%或約50%。一些實施例中，在增加相對溼度的同時，該等電漿流出物可持續流進處理區域。於操作435，隨後可移除額外量的暴露氧化物。透過在移除期間增加處理區域內的相對溼度，可移除額外量的氧化物，而可容許該製程有額外的優點，該優點會在下文中進一步描述。
用在該方法中的前驅物可包括含氟前驅物或含氫前驅物。示範性含氟前驅物可為三氟化氮（NF3 ），該三氟化氮可流進遠端電漿區域，該遠端電漿區域可與處理區域分開但流體耦接。可與三氟化氮一併使用氟的其他來源，或用氟的其他來源取代三氟化氮。大致上，含氟前驅物可流進遠端電漿區域，且該含氟前驅物可包括至少一種前驅物，該前驅物選自由下述構成之群組：原子氟、二原子氟、三氟化氮、四氟化碳、氟化氫、二氟化氙、及各種其他用於半導體處理或可用於半導體處理的含氟前驅物。該等前驅物亦可包括任何數目的載氣，該載氣可包括氮氣、氦氣、氬氣、或其他稀有、惰性、或實用前驅物。
該含氫前驅物可包括氫、碳氫化合物、水、過氧化氫、或熟悉此技藝者會瞭解的可包括氫的其他材料。亦可伴隨第二前驅物納入諸如載氣或惰性材料之類的額外前驅物。該等前驅物之一或多者可繞過遠端電漿區域並且流進處理腔室之額外區域。這些前驅物可在處理區域或腔室的某些其他區域中與電漿流出物混合。例如，當含氟前驅物流過遠端電漿區域以產生含氟電漿流出物時，該含氫前驅物可繞過遠端電漿區域。該含氫前驅物可透過腔室頂部的旁路（bypass）繞過遠端電漿區域，或是可流進腔室的分開的區域，諸如通過提供進出噴頭內之容積的通口，該噴頭諸如為第2圖的噴頭225。含氫前驅物可隨後流進處理區域，在該處，該前驅物可隨後與含氟電漿流出物混合或交互作用。多個實施例中，在移除操作期間該電漿處理區域可維持無電漿。無電漿是意味，操作期間在處理區域內可不主動地形成電漿，然而在該等操作期間可使用如先前所述之遠端產生的電漿流出物。
可參考第 5A 圖至第5C 圖 進一步瞭解本技術的額外態樣。第5圖顯示根據本技術之多個實施例處理的基板的剖面視圖。以第5A圖開始，圖中顯示上面可利用本技術的基板的剖面視圖。舉例而言，矽基板505可具有形成或界定於其表面內的一或多個特徵，諸如所說明的溝槽510。本技術所涵蓋的多個實施例中，溝槽510可由反應性離子蝕刻製程形成，然而類似地涵蓋可形成溝槽與其他特徵的其他的蝕刻製程。溝槽510可為如先前所論述的高深寬比溝槽，且該溝槽510的深寬比可為大於10、大於50、大於100、或在這些數目之任一者內或如可形成更深、更窄的溝槽的其他數目。
在其中已使用反應性離子蝕刻而形成溝槽510的示範性情況中，氧化物硬遮罩515可形成於基板505之表面上。此外，殘餘材料520可形成於溝槽510內或留在該溝槽510內，該殘餘材料520可包括碳、氧、或來自蝕刻的其他雜質。可執行製程的操作（諸如上文所述之製程400的所選操作）以從矽基板505之表面移除暴露氧化物材料。舉例而言，含氟前驅物的電漿流出物以及含氫前驅物可遞送至處理區域，以至少部分移除氧化物硬遮罩515以及殘餘材料520。因為溝槽510及任何其他特徵可能具有高深寬比，所以在多個實施例中可將處理區域內的相對溼度維持在低於約50%。透過將相對溼度維持在低於約50%，水滴可能不會沿著表面形成，水滴在乾燥或移除時可能會引發圖案變形或崩塌。
在已移除氧化物硬遮罩515及殘餘材料520之後，可能會留下氧化物薄膜。如第5B圖中所說明，氧化物材料525可存在於基板505上。舉例而言，氧化物材料525可為因暴露於空氣而遍及矽表面存在的氧化物層，或者可為氧化物硬遮罩515的殘餘部分。氧化物材料525可為氧化物薄層，該氧化物薄層可小於10nm或約10nm、小於8nm或約8nm、小於6nm或約6nm、小於5nm或約5nm、小於4nm或約4nm、小於3nm或約3nm、小於2nm或約2nm、小於1nm或約1nm、或更小。諸如與第4圖相關論述的乾蝕刻操作可能在移除氧化物525方面有困難。例如，殘餘的氧化物材料525可能在矽基板505與上方的氧化物材料525之間的界面處稍微較非晶形。在矽基質及氧化矽結構之間可能共有最終的氧原子層。一些情況中，乾蝕刻操作可能無法劈裂這些鍵結，而可能使得殘餘的氧留在該表面處，諸如具有氧化物材料525。
可包括關於第4圖所述之某些操作的乾蝕刻操作可增加基板表面位階的氟濃度。當乾蝕刻無法從矽表面劈裂最終的氧層時，用於蝕刻劑中的氟可鍵結或連結該氧化物材料525。溼蝕刻在用於較低深寬比特徵時，可能不會如乾蝕刻在基板內保留氟的量，但溼蝕刻可能無法維持高深寬比特徵，且可能由於表面張力而引發圖案崩塌。殘餘的氟可作為影響元件功能的雜質。例如，溝槽或特徵可能例如在記憶體元件的製造中形成。在該等單元形成前，可能要尋求相對或實質上純的基板表面。雜質可能增加來自元件的漏電流，而可能轉而增加電力耗損，且由於增加恢復速率以維持記憶資料免於漏損而造成電池壽命減少。
氧化物材料525可使基板內表面位階濃度的氟得以增加。附接至氧化物材料525或該氧化物525內所含的氟在該基板的某些區域（諸如中央區域）可多達或大於8原子%。將由於此雜質造成的漏電流減至最少的期望氟水準可為低於3%或約3%，此為舉例。這樣水準的氟的併入可透過溼蝕刻產生，但當特徵尺寸減少，溼蝕刻可能引發圖案崩塌及元件失效。但本技術可利用相對溼度及/或一或多個其他條件（下文中論述），以將氟的表面位階濃度減少至低於其他乾蝕刻製程。
如上文針對第4圖所述，可將處理腔室內的相對溼度增加至超過約50%。透過增加相對溼度，可從矽表面移除額外的氧材料，而可移除可能與氧連結的殘餘的氟。透過減少氟的原子百分比，可減少漏電流，且可改善元件效能。然而，發明人已另外確定，可以一系列的操作執行該等操作，該一系列的操作先移除氧化物材料之巨量部分（bulk portion），之後再增加相對溼度。如果一開始將相對溼度增加至超過50%，則可能發生某些問題。在夠高的相對溼度，水滴可能會形成在基板表面上，而隨後可能引發圖案崩塌或變形，如上文所解釋。甚至是單層的液態水都已顯示會產生圖案變形或崩塌。
此外，以乾蝕刻劑移除期間的氧硬遮罩可能產生氟化矽。然而，利用水，可從該氧硬遮罩產生氟矽酸，而可能由於相對發黏的黏稠度而引發圖案崩塌。因此，正在移除氧化物硬遮罩時，可在較低的相對溼度（諸如約25%的相對溼度，此為舉例）執行該等操作，以移除硬遮罩材料的主要部分。其他實施例中，可將該相對溼度維持在低於50%或約50%、低於45%或約45%、低於40%或約40%、低於35%或約35%、低於30%或約30%、低於25%或約25%、低於20%或約20%、低於15%或約15%、低於10%或約10%、或更低。該相對溼度亦可維持在這些數值的任一者之間，或維持在涵蓋在這些範圍內的任何更小的範圍。
當已充分減少殘餘氧化物材料（諸如減少至低於幾奈米或更低的閾值）時，或是當蝕刻操作可能不會移除額外氧化物材料時，可將相對溼度增加至超過約50%。增加的相對溼度可使額外氧得以移除，且使可與該氧化物連結或附接的氟亦得以移除。多個實施例中，可將該相對溼度增加至超過50%或約50%，且亦可增加至超過55%或約55%、超過60%或約60%、超過65%或約65%、超過70%或約70%、超過75%或約75%、超過80%或約80%、超過85%或約85%、超過90%或約90%、超過95%或約95%，或更高，然而於100%的相對溼度下，液態水可能存在，而可能引發圖案崩塌或變形。因此，該相對溼度可維持在低於100%或約100%、介於其餘所述百分比之任一者之間、或是在所述範圍內的任何更小範圍之內。
如第5C圖中所說明，所增加的相對溼度可使額外氧化物材料525得以從基板505移除，而可使所併入的氟得以移除。本技術可類似地用於移除可能在基板上的氧薄層或氧化物薄層（諸如因暴露空氣所致），而不需要有移除該硬遮罩材料的操作。舉例而言，可能已暴露至空氣的實質上乾淨的基板可具有方法400之某些操作，執行這些操作以為了在額外處理之前進一步清潔該基板，諸如以類似第5B圖所說明的基板類似的基板開始。
轉至第 6 圖 ，該圖顯示一圖表，該圖表說明根據本技術之多個實施例的與相對溼度相關的元素表面濃度。該圖表說明以增加溼度執行的方法400之所選操作。例如，基板（諸如矽基板）可具有氧化物材料之薄層，諸如第5B圖中所說明的層525。含氫前驅物（諸如水蒸氣）可伴隨含氟前驅物之電漿流出物遞送至半導體處理腔室之處理區域。第6圖顯示菱形605，該菱形605對應矽基板內（諸如在基板表面處的殘餘氧化物材料內）的氟濃度。第6圖亦包括方塊610，該方塊610對應矽基板內（諸如在表面位階的氧化物材料）的氧濃度。如第6圖中所說明，移除操作可不完全移除氧化物材料。三角形615說明基板表面上殘餘氧化物材料的真實厚度。如所說明，該厚度在硬遮罩移除後可小於1nm，諸如約6Å。
第6圖亦說明隨著相對溼度增加至超過25%，該氟濃度稍微減少，同時氧濃度及氧化物厚度實質上維持住。然而，隨著相對溼度增加至超過約50%的相對溼度，發生逐步的改變，且氧濃度、氧化物厚度、及氟濃度都減少了。氟濃度可減少至低於約2%，而可提供適當的元件品質及漏損效應。因此，第6圖說明本技術如何利用增加的相對溼度減少基板內的氟濃度且同時維持基板上的特徵。用於產生第6圖的元件維持遍及基板的臨界尺寸，例如高深寬比特徵並未實質上減少，且遍及基板上未發生圖案變形及崩塌。多個實施例中，基板的臨界尺寸（諸如或包括高深寬比特徵寬度）可在多個實施例中減少小於10%，且可減少小於8%或約8%、小於6%或約6%、小於5%或約5%、小於4%或約4%、小於3%或約3%、小於2%或約2%、小於1%或約1%、或可實質上或基本上由本技術所維持。
製程的條件亦可能影響方法400中執行的操作以及根據本技術的其他移除方法。多個實施例中，方法400的操作的各者可在恆溫期間執行，然而在一些實施例中，不同操作期間可調整該溫度。舉例而言，多個實施例中，在方法400期間該基板、底座、或腔室溫度可維持在低於50°C或約50°C。該基板溫度可維持在低於45°C或約45°C、低於40°C或約40°C、低於35°C或約35°C、低於30°C或約30°C、低於25°C或約25°C、低於20°C或約20°C、低於15°C或約15°C、低於10°C或約10°C、低於5°C或約5°C、低於0°C或約0°C、低於-5°C或約-5°C、或更低。然而，一些實施例中，可將溫度維持在超過0°C或約0°C以防止含氫前驅物（可為水）凍結。該溫度亦可維持在這些範圍內的任何溫度、這些範圍所涵蓋的較小範圍，或在這些範圍的任一者之間。
一些實施例中，可在第一溫度執行第一移除操作425，而可在第二溫度執行額外的移除操作435。該等溫度之任意一者或兩者可在上述的範圍之任一者內。多個實施例中，第二溫度可低於第一溫度。舉例而言，在相對溼度增加期間，基板溫度可從第一溫度降低至第二溫度。透過降低基板溫度，亦可增加晶圓位階處的相對溼度，而不須添加實質更多水蒸氣至處理腔室。隨後可減少水滴在腔室部件上或在基板上形成的機率，而可助於減少或防止圖案變形或崩塌。
例如，多個實施例中，第一溫度可大於10°C或約10°C，且第二溫度可小於10°C或約10°C。一些實施例中，該第一溫度可介於約10°C至約20°C之間、介於約11°C至約18°C之間、介於約12°C至約15°C之間、或在多個實施例中可為約12°C、約13°C、約14°C、或約15°C。此外，多個實施例中，該第二溫度可介於約0°C至約10°C之間、介於約1°C至約8°C之間、介於約2°C至約5°C之間、或在多個實施例中可為約2°C、約3°C、約4°C、或約5°C。第一溫度與第二溫度之間的溫度減少在多個實施例中可為至少約2°C，且可為至少3°C或約3°C、至少4°C或約4°C、至少5°C或約5°C、至少6°C或約6°C、至少7°C或約7°C、至少8°C或約8°C、至少9°C或約9°C、至少10°C或約10°C、至少11°C或約11°C、至少12°C或約12°C、或更大。此外，溫度減少小於15°C或約15°C，或在這些範圍之任一者之間的任何更小範圍，或是這些範圍的任一者內。
腔室內的壓力亦可影響所執行的操作，且在多個實施例中該腔室壓力可維持在低於約50托耳、低於40托耳或約40托耳、低於30托耳或約30托耳、低於25托耳或約25托耳、低於20托耳或約20托耳、低於15托耳或約15托耳、低於10托耳或約10托耳、低於5托耳或約5托耳、低於1托耳或約1托耳、或更小。該壓力亦可維持在這些範圍內的任何壓力、這些範圍所涵蓋的較小範圍內、或這些範圍的任一者之間。
一些實施例中，可在第一壓力執行第一移除操作425，而可在第二壓力執行額外的移除操作435。該等壓力之任意一者或兩者可在上述的範圍之任一者內。多個實施例中，第二壓力可高於第一壓力。舉例而言，在相對溼度增加期間，基板壓力可從第一壓力增加至第二壓力。透過增加腔室內的基板壓力，亦可增加晶圓位階處的相對溼度，而不須添加實質更多水蒸氣至處理腔室。隨後可減少水滴在腔室部件上或在基板上形成的機率，而可助於減少或防止圖案變形或崩塌。
舉例而言，多個實施例中，第一壓力可小於10托耳或約10托耳，且第二壓力可大於10托耳或約10托耳。一些實施例中，第一壓力可介於約0托耳至約10托耳之間、介於約3托耳至約9托耳之間、介於約5托耳至約8托耳之間，或在多個實施例中可為約5托耳、約6托耳、約7托耳、或約8托耳。多個實施例中，該第二壓力可介於約10托耳至約20托耳之間、介於約10托耳至約18托耳之間、介於約11托耳至約15托耳之間，或在多個實施例中可為約11托耳、約12托耳、約13托耳、約14托耳、或約15托耳。多個實施例中，第一壓力及第二壓力之間的壓力增加可為至少約1托耳，且於多個實施例中可為至少2托耳或約2托耳、至少3托耳或約3托耳、至少4托耳或約4托耳、至少5托耳或約5托耳、至少6托耳或約6托耳、至少7托耳或約7托耳、至少8托耳或約8托耳、或更大。該壓力增加在多個實施例中可小於10托耳或約10托耳，或可為在這些範圍之任一者內的更小範圍，或是介於這些範圍之任一者之間。
該等前驅物之一或多者的流速可與其他處理條件一併調整。例如，可減少含氟前驅物之流速，同時增加處理腔室內的相對溼度，然而在一些實施例中，可維持或增加該流速。方法400的操作的任一者中，該含氟前驅物之流速可介於約2sccm至約100sccm之間。此外，該含氟前驅物之流速可為至少2sccm或約2sccm、至少3sccm或約3sccm、至少4sccm或約4sccm、至少5sccm或約5sccm、至少6sccm或約6sccm、至少7sccm或約7sccm、至少8sccm或約8sccm、至少9sccm或約9sccm、至少10sccm或約10sccm、至少11sccm或約11sccm、至少12sccm或約12sccm、至少13sccm或約13sccm、至少14sccm或約14sccm、至少15sccm或約15sccm、至少16sccm或約16sccm、至少17sccm或約17sccm、至少18sccm或約18sccm、至少19sccm或約19sccm、至少20sccm或約20sccm、至少25sccm或約25sccm、至少30sccm或約30sccm、至少40sccm或約40sccm、至少50sccm或約50sccm、至少60sccm或約60sccm、至少80sccm或約80sccm、或更大。該流速亦可介於這些所述流速之任一者之間，或在這些數值之任一者所涵蓋的更小範圍內。
取決於所用的前驅物，可以這些流速之任一者使含氫前驅物流入，該等流速可為含氫前驅物之任何數值。例如，若利用水蒸氣，則水可以至少1克/分或約1克/分的速率引入。該水亦可以下述速率引入：至少2克/分或約2克/分、至少3克/分或約3克/分、至少4克/分或約4克/分、至少5克/分或約5克/分、至少6克/分或約6克/分、至少7克/分或約7克/分、至少8克/分或約8克/分、至少9克/分或約9克/分、或更大，然而可以低於約10g/分引入水，以減少部件及基板上水的冷凝。可以介於這些所述流速之任一者之間、或是這些數值之任一者涵蓋的較小範圍內的流速引入水。
完成方法400時，基板中的氟濃度在多個實施例中可為低於8%或約8%，且可為低於7%或約7%、低於6%或約6%、低於5%或約5%、低於4%或約4%、低於3%或約3%、低於2%或約2%、低於1%或約1%，或更低。類似地，基板中的氧濃度在多個實施例中可低於15%或約15%，且在多個實施例中可為低於12%或約12%、低於10%或約10%、低於9%或約9%、低於8%或約8%、低於7%或約7%、低於6%或約6%、低於5%或約5%、低於4%或約4%、低於3%或約3%、低於2%或約2%、低於1%或約1%，或更低。
一些實施例中，可增量式（incrementally）執行相對溼度的增加。舉例而言，在將前驅物遞送至處理區域的同時，可將相對溼度增加某百分比。可用一或多個增量（increment）增加相對溼度，該增量可為小於50%或約50%的相對溼度、小於40%或約40%的相對溼度、小於30%或約30%的相對溼度、小於20%或約20%的相對溼度、小於15%或約15%的相對溼度、小於10%或約10%的相對溼度、小於5%或約5%的相對溼度，或更小。亦可以介於這些數值之任一者之間或在這些範圍之任一者所涵蓋的較小範圍內的增量增加該相對溼度。此外，在多個實施例中，可將相對溼度從起始的相對溼度逐漸增加至最終的相對溼度，此操作可執行一段時間以減少過剩的水凝結發生的機率，該水凝結可能會導致圖案變形或崩塌。
轉至第 7 圖 ，該圖顯示根據本技術之多個實施例的方法700。方法700可包括先前所述之方法400的一些或所有操作、條件、參數、或結果。例如，方法700可包括，在操作705，將含氟前驅物流進半導體處理腔室的遠端電漿區域。可使該前驅物流入且同時在該遠端電漿區域內形成電漿，而生成含氟前驅物的電漿流出物。於操作710，該等電漿流出物可流入腔室的處理區域。基板可容納在處理區域內，且該基板可特點在於高深寬比特徵，該高深寬比特徵具有暴露氧化物之區域。
於操作715，當該等電漿流出物流進處理區域的同時，可將含氫前驅物流進該處理區域。多個實施例中，該含氫前驅物可繞過該遠端電漿區域。在操作720，可移除至少一部分的暴露氧化物，同時將該處理區域內的相對溼度維持在大於50%或約50%。在操作725，在至少部分的移除之後，可增加含氟前驅物之流速，同時將該處理區域內的相對溼度維持在大於50%或約50%。於操作730，可移除額外的暴露氧化物。
本技術亦可在其中相對溼度可能無法增加至超過閾值的條件中有效產生上文所述之益處。此外，協同相對溼度的增加，可增加含氟前驅物之流速，而可進一步移除額外的氧或氟材料。該方法可包括閾值相對溼度值，諸如至少約50%的相對溼度，以提供上文所述之材料的移除。對殘餘氧化物層而言，當相對溼度減少至低於50%或約50%，鍵結可能會更難以劈裂或無法劈裂，如上文所論述。
第8 圖 顯示圖表，該圖表說明根據本技術之多個實施例的與前驅物流速相關的元素之表面濃度。該圖表說明其中增加含氟前驅物之流速的本技術操作期間矽基板中併入氧與氟的效應。操作期間的相對溼度維持在約50%至約65%之間。如所說明，在增加含氟前驅物流速的同時氟濃度維持在低於約3%的併入，如方塊805所說明。隨著流速增加，先前論述的氧化物層的厚度在厚度上減少超過1埃，如三角形815所說明。此外，如菱形810所說明的氧併入是隨著流速增加而減少。在增加之前及增加之後含氟前驅物的流速可為先前論述的前驅物流速之任一者。多個實施例中，該流速可增加至至少1sccm或約1sccm、至少2sccm或約2sccm、至少3sccm或約3sccm、至少4sccm或約4sccm、至少5sccm或約5sccm、至少6sccm或約6sccm、至少7sccm或約7sccm、至少8sccm或約8sccm、至少9sccm或約9sccm、至少10sccm或約10sccm、至少11sccm或約11sccm、至少12sccm或約12sccm、至少13sccm或約13sccm、至少14sccm或約14sccm、至少15sccm或約15sccm、至少20sccm或約20sccm，或更高。
多個實施例中，該等移除操作可將氧的併入減少至低於約14%，且可將該氧的併入減少至低於12%或約12%、低於10%或約10%、低於7%或約7%、低於6%或約6%、低於5%或約5%、低於4%或約4%、低於3%或約3%、低於2%或約2%，或更低。該等移除操作亦可將該氧的併入減少至少2%或約2%，且可將該氧的併入減少至少3%或約3%、至少4%或約4%、至少5%或約5%、至少6%或約6%、至少7%或約7%、至少8%或約8%、至少9%或約9%、至少10%或約10%、至少11%或約11%、至少12%或約12%，或更多。
可在氧化物材料上執行方法700，該氧化物材料諸如第5B圖中所說明的氧化物材料525。多個實施例中，氧化物的暴露區域可特點在於小於5nm或約5nm的厚度，且可特點在於下述厚度：小於4nm或約4nm、小於3nm或約3nm、小於2nm或約2nm、小於1nm或約1nm、小於9 Å或約9Å、小於8 Å或約8Å、小於7 Å或約7Å、小於6 Å或約6Å、小於5 Å或約5Å、小於4 Å或約4Å、小於3 Å或約3Å，或更小。透過在特點在於厚度小於幾奈米或約幾奈米的氧化物材料上執行該等操作，可減少氟矽酸的效應，而可減少圖案變形或崩塌。此外，方法700可維持或限制對基板特徵尺寸或基板臨界尺寸的效應，該尺寸可減少小於5%或約5%、小於4%或約4%、小於3%或約3%、小於2%或約2%、小於1%或約1%，或該可尺寸可由該方法實質或基本上維持。
第9 圖 顯示根據本技術的多個實施例的方法900中的示範性操作。方法900可包括先前所述之方法400或方法700的一些或所有操作、條件、參數、或結果。方法900可在上文針對方法700或方法400所論述的殘餘氧化物材料上執行。例如，方法900可包括，在操作905，將含氟前驅物流進半導體處理腔室的遠端電漿區域。於操作910，可使該前驅物流入且同時在該遠端電漿區域內形成電漿，而生成含氟前驅物的電漿流出物。於操作915，該等電漿流出物可流入腔室的處理區域。基板可容納在處理區域內，且該基板可特點在於高深寬比特徵，該高深寬比特徵具有暴露氧化物之區域。
於操作920，當該等電漿流出物流進處理區域的同時，可將含氫前驅物流進該處理區域。多個實施例中，該含氫前驅物可繞過該遠端電漿區域。在操作925，可連續地使該等前驅物流過處理區域達一段時間。在操作930，在引入前驅物期間，可移除至少一部分的暴露氧化物材料。在移除期間，該處理腔室內的相對溼度可維持在大於50%或約50%（作為閾值），如上文所述。
方法900亦可在其中相對溼度可能無法增加至超過閾值的條件中有效產生上文所述之益處。此外，協同相對溼度的增加及/或含氟前驅物流速的增加，可執行氧化物材料之移除達一段時間，以進一步減少基板處的氧濃度。
第10 圖 顯示圖表，該圖表說明根據本技術之多個實施例的與經過時間相關的元素之表面濃度。將含氟電漿流出物及含氫前驅物提供至圖案化基板達一段時間，如圖所說明，該時間多達400秒。操作期間的相對溼度維持在約50%至約65%之間。如圖所說明，該方法相對地維持氟濃度，同時減少基板中的氧濃度。氟的併入由方塊1005所示，氧的併入由菱形1010所示。該圖表另外以三角形1015顯示殘餘氧化物厚度的減少。如圖所說明，方法900的移除操作可減少氧的併入至少1%或約1%，且可減少氧的併入至少2%或約2%、至少3%或約3%、至少4%或約4%、至少5%或約5%、至少6%或約6%，或更多。多個實施例中，前驅物及電漿流出物的遞送可持續至少100秒或約100秒，且可持續至少150秒或約150秒、至少200秒或約200秒、至少250秒或約250秒、至少300秒或約300秒、至少350秒或約350秒、至少400秒或約400秒、至少450秒或約450秒、至少500秒或約500秒，或更長。然而，隨著時間增加，可能會在基板中產生表面缺陷，且該等表面缺陷可能減少基板上的表面均勻度。因此，一些實施例中，可執行該等操作達少於500秒或約500秒。
上文論述的方法可容許從基板移除氧化物材料，同時限制氟的併入，並且同時維持基板特徵的臨界尺寸，該基板特徵可為高深寬比特徵。所執行的操作可包括下述一或多者：移除期間增加相對溼度、移除期間增加含氟前驅物流速、或持續該移除達一段時間，如所論述。亦可調整額外的腔室操作，如本案揭露內容全文中所論述。藉由利用本方法與操作，可清潔或蝕刻高深寬比特徵，同時不引發圖案崩塌（與溼蝕刻不同），且同時不增加或同時限制諸如氟之雜質引入（與一些習知乾蝕刻不同）。
前文的敘述中，為了解釋，已提出許多細節以提供對本技術之各種實施例的瞭解。然而，發明所屬技術領域中具有通常知識者會明瞭，可無須這些細節的其中一些，或利用額外的細節，而實行某些實施例。
已揭露許多實施例，發明所屬技術領域中具有通常知識者會瞭解，可不背離該等實施例的精神而使用各種修飾例、替代結構、及等效例。此外，並未描述許多已知的製程及元件，以避免非必要地混淆本技術。因此，上文的敘述不應視為限制本技術之範疇。此外，可將方法或製程描述為依序或分步驟，但應瞭解，可同步執行這些操作，或以與所列有別的順序執行這些操作。
提供一範圍的數值時，應瞭解除非上下文清楚地以其他方式規定，否則亦特定揭露了在該範圍之上限與下限之間的至下限之單位的最小分數的每一居中值。亦涵蓋了在所陳述的範圍中的任何陳述的值或未陳述的居中值及在該所陳述的範圍中的任何其他所陳述或居中的值之間的任何較窄範圍。該等較小範圍的上限與下限可獨立地納入該範圍中或於該範圍中排除，且其中極限值的任意一者、無一者、或兩者納入該較小範圍時的每一範圍亦涵蓋在本技術之內，但限制條件為該所陳述的範圍中有任何特定排除的極限。當所陳述的範圍包括該等極限的一者或兩者時，亦包括了排除該等所包括的極限的任意一者或兩者的範圍。
如本文及所附的申請專利範圍中所用，單數形式的「一」及「該」包括了複數個參考物，除非上下文以其他方式明確規定。因此，舉例而言，對「一前驅物」的參考對象包括了複數個此類前驅物，對「該層」的參考對象包括對一層或兩層的參考對象及發明所屬技術領域中具有通常知識者已知的其等效例，及諸如此類。
同樣，詞彙「包含」、「包括」、及「含有」用在此說明書及下文的申請專利範圍中時，希望該等詞彙指定了存在所陳述的特徵、整體、部件、或操作，但其並不排除存在或添加一或多個其他特徵、整體、部件、操作、動作、或群組。
100:處理系統 102:前開式晶圓盒 104:自動機械臂 106:低壓保持區域 108a~108f:基板處理腔室 109a~109c:串接區段 110:第二自動機械臂 200:處理腔室系統 201:遠端電漿系統 203:冷卻板 205:氣體入口組件 210:流體供應系統 214:上板 215:第一電漿區域 216:下板 217:面板 218:容積 219:流體通道 220:絕緣環 221:流體通道 223:離子抑制件 225:噴頭 233:處理區域 240:電源供應器 253:詳細視圖 255:基板 258:氣體供應區域 259:孔隙 265:基板支撐件 325:噴頭 365:貫穿孔洞 375:小孔洞 400:方法 405~435:操作 505:基板 510:溝槽 515:氧化物硬遮罩 520:殘餘材料 525:氧化物材料 605:菱形 610:方塊 615:三角形 700:方法 705~730:操作 805:方塊 810:菱形 815:三角形 900:方法 905~930:操作 1005:方塊 1010:菱形 1015:三角形
透過參考說明書的其餘部分及圖式，可進一步瞭解所揭露之技術的本質與優點。
第1圖顯示根據本技術之多個實施例的示範性處理系統的一個實施例的頂視平面圖。
第2A圖顯示根據本技術之多個實施例的示範性處理腔室的示意剖面視圖。
第2B圖顯示根據本技術之多個實施例的於第2A圖中所說明的處理腔室的一部分的詳細視圖。
第3圖顯示根據本技術之多個實施例的示範性噴頭的底視平面圖。
第4圖顯示根據本技術之多個實施例的方法中的示範性操作。
第5A圖至第5C圖顯示根據本技術之多個實施例處理的基板的剖面視圖。
第6圖顯示一圖表，該圖表說明根據本技術之多個實施例的與相對溼度相關的元素的表面濃度。
第7圖顯示根據本技術之多個實施例的方法中的示範性操作。
第8圖顯示一圖表，該圖表說明根據本技術之多個實施例的與前驅物流速相關的元素的表面濃度。
第9圖顯示根據本技術之多個實施例的方法中的示範性操作。
第10圖顯示一圖表，該圖表說明根據本技術之多個實施例的與經過時間相關的元素的表面濃度。
將該等圖式的其中多個圖式納入作為示意圖。應瞭解該等圖式只是為了說明，而非視為按照比例，除非特定陳述該等圖式為按照比例。此外，作為示意圖，該等圖式供以助於理解，而可能不包括相比於實際表象的所有態樣或資訊，且為了說明可包括額外或誇張的素材。
附圖中，類似的部件及/或特徵可具有相同的元件符號。再者，相同類型的各種部件可由下述方式區別：元件符號後跟隨著區分類似部件的字母。若在說明書中僅使用第一元件符號，則該敘述可應用至具有相同第一元件符號的類似部件之任一者，而無關該字母為何。
國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無
400:方法
405~435:操作

Claims (20)

  1. 一種蝕刻方法，包括： 將一含氟前驅物流進一半導體處理腔室的一處理區域，其中該處理區域容納一基板，該基板包括一暴露氧化物之區域； 將一含氫前驅物提供至該處理區域； 移除該暴露氧化物的至少一部分，同時將該處理區域內的相對溼度維持在低於約50%； 在移除該暴露氧化物的至少一部分之後，將該處理區域內的該相對溼度增加至大於50%或約50%；以及 移除額外量的該暴露氧化物
  2. 如請求項1所述之蝕刻方法，進一步包括：在增加該處理區域內的該相對溼度的同時，降低該基板之溫度。
  3. 如請求項2所述之蝕刻方法，其中該溫度降低至少約5°C。
  4. 如請求項1所述之蝕刻方法，進一步包括：在增加該處理區域內的該相對溼度的同時，增加該處理腔室內的壓力。
  5. 如請求項4所述之蝕刻方法，其中該壓力增加至少約1托耳。
  6. 如請求項1所述之蝕刻方法，其中該相對溼度增加至超過約65%。
  7. 如請求項1所述之蝕刻方法，其中在移除該額外量的暴露氧化物之後，該基板中的氟濃度低於5%或約5%。
  8. 如請求項1所述之蝕刻方法，其中在移除該額外量的暴露氧化物之後，該基板中的氧濃度低於8%或約8%。
  9. 如請求項1所述之蝕刻方法，其中該處理區域在該等移除操作期間維持無電漿。
  10. 如請求項1所述之蝕刻方法，其中以每增量低於20%或約20%增量式增加該相對溼度。
  11. 一種清潔方法，包括： 使一含氟前驅物流進一半導體處理腔室的一處理區域，其中該處理區域容納一基板，該基板包括一高深寬比特徵，該高深寬比特徵具有一暴露氧化物之區域； 提供一含氫前驅物至該處理區域； 移除該暴露氧化物的至少一部分，同時將該處理區域內的相對溼度維持在大於50%或約50%； 在移除該暴露氧化物的至少一部分之後，增加該含氟前驅物的流速，同時將該處理區域內的該相對溼度維持在大於50%或約50%；以及 移除額外量的該暴露氧化物。
  12. 如請求項11所述之清潔方法，其中移除額外量的該暴露氧化物將氧濃度降低至少約5%。
  13. 如請求項11所述之清潔方法，其中該含氟前驅物之流速增加至少約2sccm。
  14. 如請求項11所述之清潔方法，其中在該等移除操作前該氧化物的暴露區域的厚度為小於2nm或約2nm。
  15. 如請求項11所述之清潔方法，其中該高深寬比特徵的臨界尺寸減少小於1%或約1%。
  16. 如請求項11所述之清潔方法，其中該處理區域在該等移除操作期間維持無電漿。
  17. 一種移除方法，包括： 使一含氟前驅物流進一半導體處理腔室的一處理區域，其中該處理區域容納一基板，該基板包括一高深寬比特徵，該高深寬比特徵具有一暴露氧化物之區域； 在使該含氟前驅物流進該處理區域的同時，提供一含氫前驅物至該處理區域； 繼續使該含氟前驅物及該含氫前驅物流動進入該處理區域達至少約200秒；以及 移除該暴露氧化物的至少一部分，同時將該處理區域內的相對溼度維持在大於50%或約50%。
  18. 如請求項17所述之移除方法，其中該處理區域在該等移除操作期間維持無電漿。
  19. 如請求項17所述之移除方法，其中繼續使該含氟前驅物及該含氫前驅物流動執行達少於500秒或約500秒。
  20. 如請求項17所述之移除方法，其中該移除將該基板內的氧濃度減少至少約3%。
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