TW202129052A - 用於填充基材表面上之間隙特徵之方法及相關的半導體結構 - Google Patents
用於填充基材表面上之間隙特徵之方法及相關的半導體結構 Download PDFInfo
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Abstract
本發明揭示一種用於填充基材表面上之間隙特徵之方法。方法可包括:提供基材,基材包含非平面狀表面,表面包括一或多個間隙特徵;藉由循環沉積製程在一或多個間隙特徵之表面上方沉積金屬氧化物膜;使金屬氧化物與有機配體蒸氣接觸;及將金屬氧化物膜之至少一部分轉化成多孔材料,從而填充一或多個間隙特徵。亦揭示由本揭露之方法所形成之包括金屬有機框架材料的半導體結構。
Description
本揭露大致上係關於用於填充基材上之間隙特徵之方法,且具體係關於用於藉由循環沉積製程沉積金屬氧化物膜及隨後將金屬氧化物膜轉化成多孔膜,從而填充一或多個間隙特徵之方法。本揭露大致上亦關於半導體結構,其等包含經設置在一或多個間隙特徵中並填充該(等)間隙特徵之金屬有機框架材料。
用於形成半導體裝置結構(諸如,例如電晶體、記憶體元件、及積體電路)之半導體製造製程之範圍廣泛,並可包括沉積製程、蝕刻製程、熱退火製程、微影製程、及摻雜製程(僅舉其中一些例子)。
常用的一種特殊半導體製造製程係沉積介電膜至間隙特徵中,從而以介電材料填充間隙特徵,常稱為「間隙填充(gap fill)」的一種製程。半導體基材可包含在具有非平面狀表面之基材上的大批間隙特徵,該等間隙特徵經設置在基材表面的突出部分或形成於基材表面中的凹入之間。隨著半導體裝置結構幾何已減小且高深寬比特徵的在此類半導體裝置結構(如DRAM、快閃記憶體、及邏輯)中變得更為普遍,使用具有所欲特性之材料填充大批間隙特徵逐漸變得困難。
沉積方法(諸如高密度電漿(HDP)、次大氣化學氣相沉積(SACVD)、及低壓化學氣相沉積(LPCVD))已用於間隙填充製程,但這些製程通常並未達成所欲的間隙填充能力。流動性化學氣相沉積及旋塗介電質(SOD)方法可達成所欲的間隙填充,但欲整合這些方法係特別複雜且昂貴的,因為其等可需要額外的處理步驟。原子層沉積(ALD)製程亦已用於間隙填充,但這些製程可遭受長處理時間及低產出量,對大間隙尤是。在一些情況下,使用多步驟沉積製程,包括沉積-蝕刻-沉積製程,其等在後續的沉積操作之間需要不同的蝕刻操作。雖然沉積-蝕刻-沉積製程可用於間隙填充製程,使用不涉及蝕刻步驟的製程將係較佳的。因此,所欲的是用於在非平面狀基材上以間隙填充材料填充間隙特徵之方法及相關聯的半導體結構,其等具有改善的特性並具有簡化的製造製程。
提供本發明內容來以簡化形式介紹一系列概念。此等概念在以下揭示內容之例示性實施例之詳細描述中加以進一步詳述。本發明內容並非意欲鑑別所主張之主題的關鍵特徵或基本特徵,亦非意欲用以限制所主張之主題的範疇。
在一些實施例中,提供用於填充基材表面上之間隙特徵之方法。方法可包含:提供包含非平面狀表面之基材,表面包括一或多個間隙特徵;藉由循環沉積製程在一或多個間隙特徵之表面上方沉積金屬氧化物膜;使金屬氧化物膜與有機配體蒸氣接觸;及將金屬氧化物膜之至少一部分轉化成多孔材料,從而填充多個間隙特徵之一。
在一些實施例中,提供半導體結構。半導體結構可包含:基材,其包含非平面狀表面,表面包括一或多個間隙特徵;及金屬有機框架材料,其經設置在一或多個間隙特徵中並填充一或多個間隙特徵。
出於概述本發明及所達成之優於先前技術之優點的目的,已在上文中描述本發明之某些目標及優點。當然,應理解,可無須根據本發明之任何特定實施例來達成所有此類目標或優點。因此,舉例而言,熟悉本技藝者應認識到,本發明可以如本文所教示或建議達成或最佳化一個優點或一組優點而無須達成如本文可能教示或建議之其他目標或優點的方式實施或執行。
此等實施例之全部係意欲屬於本文所揭示之本發明的範疇。此等及其他實施例將自以下參見附圖的某些實施例之詳細描述而對本發明所屬技術領域中具有通常知識者變得顯而易見,但本發明並不受限於所揭示之任何一或多個特定實施例。
雖然在下文揭示某些實施例及實例,所屬技術領域中具有通常知識者將了解本發明延伸超出本發明及其明顯的修改與等同物之具體揭示的實施例及/或用途。因此,希望所揭示之本發明之範疇不應受下文所描述之特定揭示之實施例限制。
本文呈現之圖示並不意欲為任何特定材料、結構或裝置之實際視圖,而僅係用於描述本揭示之實施例的理想化表示。
如本文中所使用,用語「循環沉積(cyclic deposition)」可指將前驅物(反應物)循序引入反應室中以在基材上方沉積膜,並包括沉積技術,諸如原子層沉積及循環化學氣相沉積。
如本文所用,用語「循環化學氣相沉積(cyclical chemical vapor deposition)」可指使基材依序暴露於兩種或更多種揮發性前體的任何製程,揮發性前體在基材上反應及/或分解以產生所需沉積。
如本文所用,用語「基材(substrate)」可指可使用的或上面可形成裝置、電路或膜的任何一或多種下層材料。
如本文所用,用語「原子層沉積(atomic layer deposition)」(ALD)可指其中在反應室中進行沉積循環、較佳複數個連續沉積循環的氣相沉積製程。通常,在每個循環期間,前驅體化學吸附至沉積表面(例如,基材表面或先前沉積的下層表面,諸如來自先前ALD循環的材料),由此形成不易與額外前驅體反應的單層或亞單層(亦即,自限性反應)。其後,若有必要,可隨後將反應物(例如,另一前驅物或反應氣體)引入至製程室中,以用於在沉積表面上將經化學吸附之前驅物轉化成所欲材料。一般而言,此反應物能夠進一步與前驅物起反應。進一步地,亦可在各循環期間利用沖洗步驟以從製程室移除過量前驅物及/或在轉化經化學吸附之前驅物之後從製程室移除過量反應物及/或反應副產物。進一步地,當使用(多個)前驅物組成物、反應性氣體、及沖洗(例如惰性載體)氣體的交替脈衝執行時,如本文中所使用之用語「原子層沉積(atomic layer deposition)」亦意指包括由相關用語指定的製程,諸如「化學氣相原子層沉積(chemical vapor atomic layer deposition)」、「原子層磊晶(atomic layer epitaxy)」(ALE)、分子束磊晶(MBE)、氣體源MBE、或有機金屬MBE、及化學束磊晶。
如本文中所使用,用語「膜(film)」可指藉由本文所揭示之方法沉積之任何連續或不連續的結構或(多個)材料。例如,「膜(film)」可包括2D材料、奈米棒、奈米管、奈米層壓體、或奈米粒子、或甚至部分或完整分子層、或部分或完整原子層、或原子及/或分子團簇。
如本文中所使用,用語「間隙特徵(gap feature)」可指經設置在非平面狀表面的一或多個傾斜表面之間的開口或孔穴。用語「間隙特徵(gap feature)」可指經設置在垂直地延伸自基材表面之兩突起部的(多個)相對傾斜側壁之間的開口或孔穴。用語「間隙特徵(gap feature)」可指經設置在垂直地延伸至基材表面中之凹入的一或多個相對傾斜側壁之間的開口或孔穴。
如本文中所使用,用語「金屬氧化物(metal oxide)」可指包括金屬成分及氧成分兩者的材料。
如本文中所使用,用語「有機蒸氣配體(organic vapor ligand)」可指氣相有機分子或離子,其可結合至金屬物種以形成配位錯合物。
如本文中所使用,用語「多孔材料(porous material)」可指包含複數個孔洞的材料。
如本文中所使用,用語「金屬有機框架(metal-organic framework)」可指包含配位至具有多於一個配位基之有機配體的金屬離子或金屬離子團簇之多孔材料。在本文中,為了簡明之故,用語「金屬有機框架(metal-organic framework)」(MOF)亦涵蓋由本文所述之方法製造之配位聚合物,其可係非晶及/或非多孔材料,其中一般將「金屬有機框架(metal-organic framework)」視為結晶材料。配位聚合物可係無機或有機金屬結構,其包含(多個)聚合物且亦含有以配體聯結之金屬陽離子中心。可將配位聚合物視為具有在1、2、或3維延伸之重複的配位實體之配位化合物。配位聚合物亦可描述為聚合物,其重複單位包含配位錯合物。如此處在描述MOF的實施例中所陳述的,其亦包含配位聚合物。
如本文中所使用,用語「縫(seam)」可指由間隙填充材料中所形成之邊緣之毗連形成的線或者一或多個孔洞,且「縫」可使用掃描穿透電子顯微鏡(STEM)或穿透電子顯微鏡(TEM)來確認,其中若觀察顯示在間隙填充材料特徵中之清楚的垂直線或者一或多個垂直孔洞,則「縫」存在。
如本文中所使用,用語「無縫(seamless)」可指經設置在間隙、溝槽、或貫孔、或其他三維特徵中的間隙填充材料不具有縫。
如本文中所使用,用語「針孔(pin-hole)」可指延伸通過材料厚度的孔穴,且「無針孔(pin-hole free)」可指材料不具有針孔。
在本揭露之所有實施例中給定一些實例材料,應注意針對實例材料之各者所給定之化學式不應解釋為限制性,且所給定之非限制性實例材料不應受給定的實例化學計量限制。
本揭露包括可用於填充設置在基材之非平面狀表面之上或之中的一或多個間隙特徵之方法。間隙填充製程可包含藉由循環沉積製程在基材之非平面狀表面上方沉積金屬氧化物膜及後續藉由使金屬氧化物膜與有機配體蒸氣接觸而將金屬氧化物膜轉化成多孔材料,從而將金屬氧化物膜的至少一部分轉化成多孔材料。多孔材料可具有低於金屬氧化物膜的莫耳密度或體積質量密度,且因此隨著金屬氧化物轉化成多孔材料,膜膨脹可發生,膨脹得出在不需要額外沉積製程的情況下填充一或多個間隙特徵之多孔膜。
一或多個間隙特徵(諸如,例如一或多個溝槽)的填充係重要的半導體製造製程。因此,新式有效率且具成本效益的間隙填充製程係高度所欲的。本揭露包含實施例,其中金屬氧化物膜可經沉積,且後續至少部分地轉化成多孔材料,從而填充一或多個間隙特徵。多孔材料可包含金屬有機框架(MOF)材料,其等係一類混合式有機-無機結晶多孔材料,包含由多主題有機聯結劑以使得孔形成在晶體結構中之方式連接的金屬離子或金屬離子團簇。MOF材料的材料特性可依據若干因素調整,包括,但不限於金屬氧化物膜的組成、有機配體蒸氣的選擇及轉化製程的參數。作為一非限制性實例,多孔材料中的孔之大小可係可調整的,允許多孔材料之介電常數的可調性。此外,MOF材料可藉由多孔材料之內表面的官能化來進一步改質。
因此,本揭露之實施例可包括用於填充基材表面上之間隙特徵之方法。在一些實施例中,方法可包含:提供包含非平面狀表面之基材,表面包括一或多個間隙特徵;藉由循環沉積製程在一或多個間隙特徵之表面上方沉積金屬氧化物膜;使金屬氧化物膜與有機配體接觸;及將金屬氧化物膜之至少一部分轉化成多孔材料,從而填充一或多個間隙特徵。
本揭露之實施例可參照下列圖式更詳細地描述:圖1,其繪示用於填充一或多個間隙特徵之非限制性例示性製程流程100;圖2,其繪示代表在用於填充間隙特徵的製程中用作子製程之循環沉積製程120的非限制性例示性製程;圖3A至圖3C,其等繪示藉由本文所述之間隙填充製程形成之半導體結構的截面示意圖;及圖4A至圖4E,其等繪示藉由本文所述之間隙填充製程形成之額外半導體結構的截面示意圖。
更詳細地,例示性間隙填充製程100(圖1)可經由製程110來開始,製程包含提供包含非平面狀表面的基材,表面包括一或多個間隙特徵。
在本揭露之一些實施例中,基材(諸如圖3A的基材302)可包含一或多個材料,包括但不限於矽(Si)、鍺(Ge)、鍺錫(GeSn)、矽鍺(SiGe)、矽鍺錫(SiGeSn)、碳化矽(SiC)、或III-V族半導體材料(諸如,例如砷化鎵(GaAs)、磷化鎵(GaP)、或氮化鎵(GaN))。在本揭露之一些實施例中,基材302可包含工程基材,其中表面半導體層經設置在塊體支撐件上方,其間設置有中介埋入式氧化物(BOX)。
在一些實施例中,基材302可包括半導體裝置結構,結構形成至基材表面之中或之上,例如,基材可包含部分製造的半導體裝置結構(諸如,例如電晶體及/或記憶體元件)。在一些實施例中,基材可含有單晶表面及/或可包含非單晶表面(諸如多晶表面及/或非晶表面)之一或多個二次表面。單晶表面可包含例如矽(Si)、矽鍺(SiGe)、鍺錫(GeSn)、或鍺(Ge)中之一或多者。多晶或非晶表面可包括介電材料(諸如氧化物、氮氧化物、或氮化物,諸如,例如氧化矽及氮化矽)。
在本揭露之一些實施例中,基材302可包含包括一或多個間隙特徵304之非平面狀表面(諸如上部經暴露表面)。
在一些實施例中,基材302可包含複數個突起部,且在此類實施例中,間隙特徵304可包含經設置在垂直地延伸自基材302之表面的兩相鄰突起部之相對傾斜側壁306A與306B之間的開口或孔穴。在一些實施例中,複數個突起部可包含與基材302相同的材料,而在替代實施例中,複數個突起部可包含不同於基材302的材料。
在一些實施例中,基材302可包含複數個凹入,且在此類實施例中,間隙特徵304可包含經設置在垂直地延伸至基材302之表面中的凹入之傾斜側壁306A與306B之間的開口或孔穴。
在本揭露之一些實施例中,一或多個間隙特徵304可具有大於2:1、或大於5:1、或大於10:1、或大於25:1、或甚至大於50:1的最大深寬比(高度:寬度)。在一些實施例中,一或多個間隙特徵304可具有小於50:1、或小於25:1、或小於10:1、或小於5:1、或小於2:1、或甚至小於1:1的最小深寬比。
例示性間隙填充製程100可經由製程方塊120來繼續,製程方塊包含藉由循環沉積製程在一或多個間隙特徵的表面上方沉積金屬氧化物膜。
循環沉積製程之一非限制性實例實施例可包括原子層沉積(ALD),其中ALD係基於一般自限制反應,藉此反應物之循序且交替的脈衝係用以在每沉積循環沉積約材料的一個原子(或分子)單層。沉積條件及前驅物一般係經選擇以提供自飽和反應,使得反應物的經吸附層留下不與相同反應物之氣相反應物起反應的表面終端。隨後,使基材與不同的前驅體接觸,不同的前驅體與先前的終端反應而實現繼續沉積。因此,交替脈衝的各循環一般留下所欲材料的不多於約一個單層。然而,如上文所提及,在所屬領域中具有通常知識者將認知到在一或多個ALD循環中可沉積超過一個材料單層(例如,若無視於製程的交替本質而發生一些氣相反應的話)。
用於沉積金屬氧化物膜之循環沉積製程可包含至少一單位循環,其中一個單位循環可包含使基材暴露至第一前驅物、將任何未經反應的第一前驅物及反應副產物從反應室移除、及使基材暴露至第二前驅物,隨後進行第二移除步驟。在一些實施例中,循環沉積循環的第一前驅物可包含金屬氣相前驅物(「金屬前驅物」),且循環沉積循環的第二前驅物可包含氧化前驅物(「氧化前驅物」)。
可藉由諸如氬(Ar)或氮(N2
)之惰性氣體來分開前驅物,以防止前驅物之間的氣相反應並致能自飽和表面反應。然而,在一些實施例中,可移動基材以分開地接觸第一前驅物及第二前驅物。由於反應自飽和,可不需要基材之嚴格的溫度控制及前驅物之精確的劑量控制。然而,基材溫度較佳地使得入射氣體物種不會冷凝成單層,亦不會在表面上分解。在使基材與下一反應性化學品接觸之前,諸如藉由沖洗反應空間或藉由移動基材來從基材表面移除過剩的化學品及反應副產物(若有的話)。可在惰性沖洗氣體的協助下從反應空間有效地排除非所欲的氣態分子。真空泵可用以協助沖洗。
能夠用以沉積金屬氧化物膜之反應器可用於本文所述之沉積製程。此類反應器包括經組態以提供前驅物之ALD反應器以及CVD反應器。根據一些實施例,可使用噴淋頭反應器。根據一些實施例,可使用交叉流式、批式、小型批式、或空間式ALD反應器。
在本揭露之一些實施例中,可使用批式反應器。在一些實施例中,可使用垂直批式反應器。在其他實施例中,批式反應器包含小型批式反應器,其經組態以容納10或更少個晶圓、8或更少個晶圓、6或更少個晶圓、4或更少個晶圓、或2或更少個晶圓。在其中使用批式反應器之一些實施例中,晶圓間之不均勻性小於3%(1σ)、小於2%、小於1%、或甚至小於0.5%。
本文所述之循環沉積製程且具體係間隙填充製程可選地可在經連接至叢集工具之反應器或反應室中實行。在叢集工具中,由於各反應室專用於一種類型的製程,所以各模組中之反應室的溫度可保持恆定,相較於在各運轉之前將基材在其中加熱至製程溫度的反應器,其改善產出量。額外地,在叢集工具中,可能會減少在基材之間將反應室抽泵至所欲之製程壓力位準的時間。在本揭露之一些實施例中,沉積製程可在叢集工具中執行,該叢集工具包含多個反應室,其中各個別的反應室可用以使基材暴露至個別的前驅物氣體,且基材可在不同的反應室之間傳遞以用於暴露至多個前驅物氣體,基材傳遞係在受控的周圍下執行以防止基材的氧化/污染。例如,第一反應室可經組態用於執行循環沉積製程以用於沉積金屬氧化物膜,且第二反應室可經組態用於後續使金屬氧化物膜與有機配體蒸氣接觸。
獨立式反應器可配備有負載鎖定件(load-lock)。在上述情況下,則不必在各運轉之間冷卻反應室。在一些實施例中,用於沉積金屬氧化物膜(諸如氧化鋅膜)的沉積製程可包含複數個沉積循環(亦即,複數個單位循環,例如ALD循環或循環CVD循環)。
在一些實施例中,可使用循環沉積製程以在非平面狀基材上沉積當前揭示的金屬氧化物膜,且循環沉積製程可包含一或多個ALD型製程。在一些實施例中,循環沉積製程可包含混合式ALD/CVD或循環CVD製程。例如,在一些實施例中,ALD製程與CVD製程相比可係低生長率的。一個增加生長率的方法可在於以高於一般ALD製程中所用的基材溫度進行操作,導致至少一部分的沉積由化學氣相沉積型製程提供,但仍利用循序引入前驅物,此一製程可稱為循環CVD。
在本揭露之一些實施例中,可使用循環沉積製程以沉積包含金屬成分及氧成分之金屬氧化物膜,並可參照圖2瞭解此循環沉積製程之一非限制性實例,該圖繪示用於沉積金屬氧化物膜之例示性循環沉積製程120,循環沉積製程120係例示性間隙填充製程100(圖1)之子製程。
更詳細地,例示性循環沉積製程120可始於將具有非平面狀表面的基材提供至反應室中及將基材加熱至所欲的沉積溫度。
用於沉積之反應室可係原子層沉積反應室、或化學氣相沉積反應室、或如本文先前所述之反應室中之任何者。在本揭露之一些實施例中,基材可在循環沉積製程期間加熱至所欲的沉積溫度。例如,基材可加熱至低於大約750°C、或低於大約650°C、或低於大約550°C、或低於大約450°C、或低於大約350°C、或低於大約250°C、或甚至低於大約150°C之基材溫度。在本揭露之一些實施例中,循環沉積製程期間之基材溫度可介於300 °C與750 °C之間、或介於400 °C與600 °C之間、或介於400 °C與450 °C之間。基材一經加熱至所欲的沉積溫度,例示性循環沉積製程120可經由製程方塊122來繼續,該方塊包含使基材與金屬氣相前驅物接觸。在本揭露之一些實施例中,金屬氣相前驅物可包含選自包含鋅(Zn)、鋯(Zr)、鋁(Al)、銅(Cu)、或鐵(Fe)之群組的金屬。在一些實施例中,金屬氣相反應物可包括金屬鹵化物氣相前驅物(諸如,例如金屬氯化物氣相前驅物、金屬碘化物氣相前驅物、或金屬溴化物氣相前驅物)。在一些實施例中,金屬氣相反應物可包含金屬鹵化物氣相前驅物(諸如ZrCl4
、ZnCl2
、AlCl3
、CuCl、或FeCl3
)。
在一些實施例中,金屬氣相前驅物可包含金屬有機氣相前驅物。在一些實施例中,金屬有機氣相前驅物可包含金屬有機或有機金屬鋅前驅物(亦即,包含鋅元素之金屬有機前驅物)。在一些實施例中,金屬有機鋅前驅物可包含二甲基鋅(ZnMe2
)、二乙基鋅(ZnEt2
)、甲基鋅異丙醇鹽(ZnMe(OPr))、或醋酸鋅(Zn(CH3
CO2
)2
)之至少一者。
在一些實施例中,金屬有機氣相前驅物係選自由下列所組成之群組的一或多者:(MeCp)2
Zr(OMe)2
、(MeCp)2
Zr(OMe)Me、四(乙甲基)胺基鋯(TEMAZr)、四(二甲基)胺基鋯(TDMAZr)、四(二乙基)胺基鋯(TDEAZr)、或三(二甲胺基)環戊二烯鋯、或其等之衍生物。
在一些實施例中,金屬有機氣相前驅物可包含金屬有機或有機金屬鋁前驅物。在一些實施例中,金屬有機氣相前驅物係選自由下列所組成之群組的一或多者:三甲基鋁(TMA)、三乙基鋁(TEA)、氫化二甲基鋁(DMAH)、異丙醇二甲基鋁(DMAI)、二甲基乙基胺鋁烷(DMEAA)、三甲基胺鋁烷(TEAA)、N-甲基吡咯啶鋁烷(MPA)、三異丙醇鋁、三異丁基鋁(TIBA)、及三三級丁基鋁(TTBA)。在一些實施例中,金屬有機氣相前驅物並非三甲基鋁(TMA)。
在一些實施例中,金屬有機氣相前驅物可包含金屬有機或有機金屬銅前驅物。在一些實施例中,銅前驅物係選自脒銅、雙(乙醯丙酮酸)銅(II)、及雙(2,2,6,6-四甲基-3,5-庚二酮基)銅(II)、及其等之衍生物。
在一些實施例中,銅前驅物係選自由銅β二酮酸鹽化合物、銅β二酮亞胺基化合物、銅胺基醇鹽化合物(諸如Cu(dmae)2
、Cu(deap)2
、或Cu(dmamb)2
)、脒銅化合物(諸如Cu(s
Bu-amd)2
)、銅環戊二烯基化合物、羰基銅化合物及其等之組合。在一些實施例中,使用Cu(acac)2
、Cu(hfac)2
、或Cu(thd)2
化合物,其中thd係2,2,6,6-四甲基-3,5-庚二酮基。Cu(acac)L、Cu(hfac)L、Cu(thd)L加合化合物,其中L係中性加合配體。在一些實施例中,不含鹵素之銅前驅物係乙酸銅(II)、[Cu(HMDS)]4
、或Cu(nhc)HMDS (1,3-二異丙基-咪唑啉-2-亞基銅六甲基二矽氮化物)、或Cu-β-二酮亞胺基(諸如Cu(dki)VTMS(dki=二酮亞胺))。
在一些實施例中,金屬有機氣相前驅物可包含金屬有機或有機金屬鐵前驅物。在本揭露之一些實施例中,金屬有機或有機金屬鐵前驅物可包含金屬有機鐵前驅物(亦即,包含鐵元素之金屬有機前驅物)。在一些實施例中,金屬有機鐵前驅物可包含鐵之環戊二烯基化合物、β二酮鐵化合物、烷基胺鐵或脒基鐵化合物、或其他金屬有機鐵化合物。在一些實施例中,金屬有機鐵前驅物可選自由下列所組成之群組:雙(N,N'-二-三級丁基乙脒基)鐵(II)、雙環戊二烯基鐵(II)、或環己二烯三羰基鐵(0)。
在本揭露之一些實施例中,使基材與金屬氣相前驅物接觸可包含將金屬前驅物脈衝至反應室中,且隨後使基材與金屬前驅物持續接觸介於約0.01秒與約60秒之間、介於約0.05秒與約10秒之間、或介於約0.1秒與約5.0秒之間的時間段。此外,在脈衝金屬前驅物期間,金屬前驅物之流量率可小於2000 sccm、或小於500 sccm、或甚至小於100 sccm。此外,在金屬前驅物於基材上方脈衝期間,金屬前驅物的流量率範圍可從約1至2000 sccm、從約5至1000 sccm、或從約10至約500 sccm。
圖2之例示性循環沉積循環120可藉由沖洗反應室來繼續。例如,過量的金屬氣相前驅物及反應副產物(若有的話)可例如藉由以惰性氣體抽泵來從基材表面移除。在本揭露之一些實施例中,沖洗製程可包含沖洗循環,其中基材表面係持續沖洗小於大約5.0秒、或小於大約3.0秒、或甚至小於大約2.0秒的時間段。過量的金屬氣相前驅物及任何可能的反應副產物可藉助於真空移除,真空係由與反應室流體連通的抽泵系統所產生。
一經以沖洗循環沖洗反應室,例示性循環沉積製程120可繼續進行製程方塊124,其包含使基材與氧化前驅物接觸。在一些實施例中,氧化前驅物包含下列之至少一者:水(H2
O)、過氧化氫(H2
O2
)、臭氧(O3)、或氮的氧化物(諸如,例如一氧化氮(NO)、氧化亞氮(N2
O)、或二氧化氮(NO2
))。在本揭露之一些實施例中,氧前驅物可包含有機醇(諸如,例如異丙醇)。在本揭露之一些實施例中,氧化前驅物可包含氧基電漿,亦即,由含氧氣體(諸如,例如分子氧(O2
)或臭氧(O3
))產生的電漿,其中氧基電漿可包含氧原子(O)、氧離子、氧自由基、及氧激發物種。
在本揭露之一些實施例中,使基材與氧化前驅物接觸可包含將氧化前驅物脈衝至反應室中,且隨後使基材與氧化前驅物持續接觸介於約0.01秒與約60秒之間、介於約0.05秒與約10秒之間、或介於約0.1秒與約5.0秒之間的時間段。此外,在氧化前驅物的脈衝期間,氧化前驅物的流量率可少於2000 sccm、或少於500 sccm、或甚至少於100 sccm。此外,在氧化前驅物於基材上方脈衝期間,氧化前驅物的流量率範圍可從約1至2000 sccm、從約5至1000 sccm、或從約10至約500 sccm。
圖2之例示性循環沉積循環120可藉由沖洗反應室來繼續。例如,過量的氧化前驅物及反應副產物(若有的話)可例如藉由以惰性氣體抽泵來從基材表面移除。在本揭露之一些實施例中,沖洗製程可包含沖洗循環,其中基材表面係持續沖洗小於大約5.0秒、或小於大約3.0秒、或甚至小於大約2.0秒的時間段。過量的氧化前驅物及任何可能的反應副產物可藉助於真空移除,真空係由與反應室流體連通的抽泵系統所產生。
圖2之循環沉積製程120可經由製程方塊126來繼續,上述方塊包含決策閘,決策閘係依據欲藉由例示性循環沉積製程120沉積之金屬氧化物膜的厚度。若所沉積之金屬氧化物膜處於對後續製程步驟而言不足的厚度,則循環沉積製程120可返回製程方塊122,且基材可與金屬氣相前驅物接觸(製程方塊122)並與氧化前驅物接觸(製程方塊124)。例如,循環沉積製程120之單一沉積循環(亦即,單位循環)可包含:使基材與金屬氣相前驅物接觸、沖洗反應室、使基材與氧化前驅物接觸、及再次沖洗反應室。欲將金屬氧化物膜沉積達所欲厚度,循環沉積製程120可重複一或多次,直到沉積金屬氧化物膜的所欲厚度,在上述時間點,例示性循環沉積製程120可經由製程方塊128來退出。
應理解,在本揭露之一些實施例中,使基材與金屬氣相前驅物及氧化前驅物接觸的順序可使得基材首先與氧化前驅物接觸,隨後與金屬前驅物接觸。此外,在一些實施例中,循環沉積製程120可包含在使基材與氧化前驅物接觸一或多次之前,使基材與金屬前驅物接觸一或多次。在一些實施例中,循環沉積製程120可包含在使基材與金屬前驅物接觸一或多次之前,使基材與氧化前驅物接觸一或多次。
在本揭露之一些實施例中,例示性循環沉積製程120交替地使基材與金屬前驅物及氧化前驅物接觸,且金屬前驅物及氧前驅物之間的反應可在基材表面上方沉積金屬氧化物膜。在本揭露之一些實施例中,金屬氧化物膜可包含氧化鋅、氧化鋯、氧化鋁、氧化銅、或氧化鐵之至少一者。在具體實施例中,由循環沉積製程120所沉積的金屬氧化物膜可包含氧化鋅。
由本文所揭示之循環沉積製程所沉積的金屬氧化物膜(諸如,例如氧化鋅)可係連續膜。在一些實施例中,金屬氧化物膜在下列厚度下可係連續的:小於大約100奈米、或小於大約60奈米、或小於大約50奈米、或小於大約40奈米、或小於大約30奈米、或小於大約20奈米、或小於大約10奈米、或甚至小於大約5奈米。本文所提及的連續性可係物理連續性或電氣連續性。在本揭露之一些實施例中,金屬氧化物膜可係物理連續的厚度可不同於金屬氧化物係電氣連續的厚度,且反之亦然。
在本揭露之一些實施例中,根據本文所述之循環沉積製程所沉積的金屬氧化物膜(例如氧化鋅、氧化鋁、氧化鋯膜、氧化銅、及氧化鐵)可具有從約20奈米至約100奈米或約20奈米至約60奈米的厚度。在一些實施例中,根據本文所述之實施例的一些者所沉積之金屬氧化物膜可具有大於約20奈米、或大於約30奈米、或大於約40奈米、或大於約50奈米、或大於約60奈米、或大於約100奈米、或大於約250奈米、或大於約500奈米、或更大的厚度。在一些實施例中,根據本文所述之實施例的一些者所沉積之金屬氧化物膜可具有小於約50奈米、或小於約30奈米、或小於約20奈米、或小於約15奈米、或小於約10奈米、或小於約5奈米、或小於約3奈米、或小於約2奈米、或甚至小於約1奈米的厚度。
在本揭露之一些實施例中,金屬氧化物膜可沉積在包含一或多個間隙特徵之基材上,如圖3B所繪示者。更詳細地,金屬氧化物膜306可設置在經設置於基材302之中或之上之多個間隙特徵304的表面上方。在一些實施例中,金屬氧化物膜306可以保形方式沉積在一或多個間隙特徵304上方,其中用語「保形(conformal)」表示金屬氧化物膜306所具有的厚度與用於金屬氧化物膜306之厚度的平均值並未有大於30%、或大於20%、或甚至大於10%的偏差。在一些實施例中,金屬氧化物膜306可沉積在一或多個間隙特徵304(亦即,高深寬比特徵)上方,其中步階覆蓋大於大約90%、或大於大約95%、或大於大約99%、或甚至實質上等於100%。如本文中所使用,用語「步階覆蓋(step coverage)」係定義為基材302之側壁上之金屬氧化物膜的厚度對基材302之水平表面上之金屬氧化物的厚度之百分比率。
作為本揭露之循環沉積製程之一非限制性實例,圖5繪示半導體結構的場發射掃描電子顯微鏡(FESEM)影像,半導體結構包括具有設置於其上之保形金屬氧化物的間隙特徵。更詳細地,圖5繪示半導體結構500,其包括矽基材502,矽基材具有包含具有大約1:1之深寬比的溝槽之間隙特徵504。直接設置在矽基材502上方,且具體直接在間隙特徵504上方的係根據本揭露之實施例沉積之大約40奈米厚的保形氧化鋅(ZnO)膜506。
一旦金屬氧化物膜已沉積達所欲厚度,例示性間隙填充製程100(圖1)可經由製程方塊130來繼續,上述方塊包含使金屬氧化物膜與有機配體蒸氣接觸以及將金屬氧化物膜的至少一部分轉化成多孔材料,從而填充一或多個間隙特徵。
更詳細地,本揭露之實施例可包含固體-蒸氣轉化製程,其中金屬氧化物係與至少一有機配體蒸氣接觸,從而將金屬氧化物膜的至少一部分轉化成多孔材料。在本揭露之一些實施例中,使金屬氧化物膜與有機配體蒸氣接觸可在用以執行循環沉積製程120的相同反應室中執行,而在替代實施例中,具有設置於其上之金屬氧化物膜的基材可傳遞至第二反應室以用於後續使金屬氧化物膜與有機配體蒸氣接觸。在基材與相關聯的金屬氧化物膜在其中於第一反應室(經組態用於循環沉積)與第二反應室(經組態用於使金屬氧化物與有機配體蒸氣接觸)之間傳遞的實施例中,第一反應室及第二反應室可整合在包含叢集工具之共同的半導體處理設備上,且第一反應室與第二反應室之間的傳遞可在受控環境下執行以防止基材及金屬氧化物膜之非所要的污染。
一旦將基材與相關聯的金屬氧化物膜設置在合適的反應室內,可將基材加熱至所欲的基材溫度以用於金屬氧化物膜至多孔材料之轉化。例如,可在使金屬氧化物膜與有機配體蒸氣接觸之前或之時,將基材加熱至低於500 °C、或低於300 °C、或於200 °C、或低於160 °C、或低於140 °C、或低於120 °C、或從約0至約300 °C、或從約20至約250 °C、或從約50至約200 °C、從約70至約160 °C、或從約80至約140 °C的溫度。
在本揭露之一些實施例中,有機配體蒸氣可包含羧酸蒸氣。在本揭露之一些實施例中,有機配體蒸氣可包含循環芳香族或脂肪族化合物。在一些實施例中,羧酸蒸氣可包含二羧酸蒸氣或三羧酸蒸氣。在一些實施例中,羧基蒸氣可包含羧酸(例如,脂肪族羧酸或芳香族羧酸,諸如1,4-苯二羧酸、2,6-萘二羧酸、或1,3,5-苯三羧酸之至少一者的蒸氣)。
在本揭露之一些實施例中,有機配體蒸氣可包含雜環化合物蒸氣,其包含氮、或硫、或氧、或其等之組合。在一些實施例中,雜環化合物蒸氣可包含五員環雜環化合物。在一些實施例中,五員環雜環化合物可包含兩個雜原子,至少一個雜原子包含氮原子。因此,在本揭露之一些實施例中,有機配體蒸氣可包含吡咯蒸氣或咪唑蒸氣,包括,但不限於2-甲基咪唑、3-(2-吡啶基)-5-(4-吡啶基-1,2,4-三吡咯)、或4,5-二氯咪唑之至少一者。
在本揭露之一些實施例中,使金屬氧化物與有機配體蒸氣接觸可包含將有機配體蒸氣脈衝至反應室中,以及隨後使基材與有機配體蒸氣持續接觸介於約0.1秒與約3600秒之間、介於約0.5秒與約1200秒之間、或介於約1秒與約600秒之間的時間段。此外,在將有機配體蒸氣脈衝至反應室中及使金屬氧化物與有機配體蒸氣接觸期間,有機配體蒸氣的流量率可小於2000 sccm、或小於1000 sccm、或甚至小於250 sccm。有機配體蒸氣可在源容器中加熱以便獲取足夠的蒸氣壓以用於輸送至反應室。在本揭露之一些實施例中,使金屬氧化物與有機配體蒸氣接觸亦可包含空氣及/或惰性氣體(諸如N2
及稀有氣體,如He及Ar)之連續流或脈衝流或靜態大氣。
例示性間隙填充製程100(圖1)之製程方塊130亦包含將金屬氧化物膜的至少一部分轉化成多孔材料,從而填充一或多個間隙特徵。在一些實施例中,使金屬氧化物膜與有機配體蒸氣接觸及將金屬氧化物的至少一部分轉化成多孔材料係同時執行,金屬氧化物膜與有機配體蒸氣之接觸產生金屬氧化物膜的至少一部分至多孔材料之轉化。換言之:使金屬氧化物膜與有機配體蒸氣接觸將金屬氧化物膜的至少一部分轉化成多孔材料。在本揭露之一些實施例中,轉化金屬氧化物膜的至少一部分包含將金屬氧化物膜完全轉化成多孔材料,亦即,金屬氧化物膜的整體厚度均轉化成多孔材料。
在本揭露之一些實施例中,金屬氧化物膜具有初始厚度,且將金屬氧化物膜的至少一部分轉化成多孔材料所產生的多孔材料在無額外沉積的情況下具有大於金屬氧化物膜之初始厚度的厚度。多孔材料可具有低於金屬氧化物膜之體積質量密度的莫耳密度,且因此隨著金屬氧化物膜轉化成多孔材料,膜膨脹可發生,膨脹得出在不需要額外沉積製程的情況下填充一或多個間隙特徵之多孔材料,如圖3C中所繪示者,其中多孔材料310填充經設置在基材302上方或之中的一或多個間隙特徵304。
在本揭露之一些實施例中,多孔材料可包含金屬有機框架(MOF)材料,其中MOF材料包含與有機配體配位的金屬成分(諸如金屬離子或金屬離子團簇)。為了簡明之故,在本揭露中,經沉積並接著至少部分地轉化成MOF或擁有小於金屬氧化物之密度之經轉化的混合式結構在本文中均視為MOF。在一些實施例中,MOF係經完全轉化的金屬氧化物框架,而在其他實施例中,MOF可僅經部分轉化。在一些實施例中,MOF材料的金屬成分可包含至少一金屬,其選自包含鋅(Zn)、鋯(Zr)、鋁(Al)、銅(Cu)、或鐵(Fe)之群組。在一些實施例中,MOF材料不包含有別於鋅(Zn)、鋯(Zr)、鋁(Al)、銅(Cu)、或鐵(Fe)之實質量(例如多於痕量(trace amounts))的其他金屬。在一些實施例中,MOF材料不包含Zn。在一些實施例中,MOF材料不包含Al作為唯一金屬。在一些實施例中,MOF材料不包含Zr作為唯一金屬。在一些實施例中,MOF材料可包含ZIF-8。在一些實施例中,MOF材料可具有小於大約4.0、或小於3.5、或小於3.0、或小於2.5、或小於2.2、或小於2.0、或小於1.8、或小於1.6、或小於1.5、或甚至小於1.4的介電常數。
本揭露之實施例可提供間隙填充製程及間隙填充材料,其等優於先前已知的方法。包括藉由常見的先前技術方法填以介電材料之間隙特徵的半導體結構之一實例係繪示於圖6。例如,圖6繪示半導體結構600的截面圖,其包含基材602(例如塊材矽),基材包含間隙特徵604,間隙特徵604經填以介電間隙填充材料606(例如二氧化矽)。如圖6所繪示,通常稱為縫608的特徵係設置在介電間隙填充材料606內。縫係指介電間隙填充材料606中的區域,其中生長自垂直間隙特徵之兩側壁的兩膜之邊緣彼此碰觸,因此縫608通常經設置在間隙特徵604的中心處。介電間隙填充材料中之縫608的形成係非所欲的,並可導致不良的裝置性能及後續在半導體裝置製造製程中的問題。縫608可包含垂直線或者一或多個巨型孔洞,其(等)可使用掃描穿透電子顯微鏡(STEM)或穿透電子顯微鏡(TEM)來觀察,其中若觀察顯示介電間隙填充材料606中之垂直線或者一或多個巨型孔洞,則縫608存在。
反之,本揭露之實施例在一或多個間隙特徵304中形成不具有縫的多孔間隙填充材料310(圖3C),亦即,經設置在一或多個間隙特徵304中之多孔材料310係無縫的。此外,在一些實施例中,本揭露之多孔間隙填充材料310可無先前的間隙填充製程及結構中常見的巨型孔洞,其中巨型孔洞與經設置在多孔間隙填充材料中的複數個孔可有所區別,因為多孔間隙填充材料中的複數個孔可包含微型或奈米孔洞。進一步地,在MOF材料的情況下,孔可係間隙填充材料之晶體結構的部分,而巨型孔洞可非間隙填充材料之結晶結構的部分。在一些實施例中,多孔間隙填充材料310可具有0.5nm至2.0nm、大於1.0nm、大於2.0nm、大於5.0nm、大於10nm、大於20nm、大於40nm的孔大小、或者從1至100nm、從2至50nm、從2至30nm、或從5至20nm的孔大小。而巨型孔洞係較大的。在一些實施例中,多孔間隙填充材料310可具有大於100 m2
/g、大於500 m2
/g、大於1000 m2
/g、大於2500 m2
/g、大於5000 m2
/g、大於7500 m2
/g、或大於10000 m2
/g的表面積。在一些實施例中,多孔間隙填充材料310可具有低於2.0 g/cm3
、低於1.5 g/cm3
、低於1.5 g/cm3
、低於1.0 g/cm3
、低於0.7 g/cm3
、低於0.5 g/cm3
、低於0.4 g/cm3
、低於0.3 g/cm3
、低於0.2 g/cm3
、低於0.15 g/cm3
的體積質量密度。
此外,在一些實施例中,多孔間隙填充材料310可包含MOF材料,且MOF材料可係連續且無針孔的,其中針孔可指延伸通過MOF材料之厚度的孔穴或洞。在一些實施例中,MOF材料填充間隙、溝槽、貫孔、或其他三維特徵(諸如凹腔結構),使得例如當以截面成像(諸如截面STEM或TEM)研究時,小於30%、小於20%、小於10%、小於5%、小於3%、小於2%、小於1%、小於0.5%、小於0.1%、小於0.05%、小於0.01%的體積或截面積未由MOF佔據(亦即,縫體積)。MOF結構之內部固有的孔穴並未視為縫。
在本揭露之一些實施例中,多孔膜310可包含MOF材料,並可形成達小於300奈米、或小於100奈米、或小於50奈米、或小於20奈米、或小於10奈米、或甚至小於5奈米的厚度。
例示性間隙填充製程100(圖1)可經由製程方塊140來繼續,上述方塊包含依據多孔材料之厚度的決策閘。若多孔材料經形成達所欲厚度從而填充一或多個間隙特徵,則例示性間隙填充製程100可經由製程方塊150來退出。在替代實施例中,多孔材料可形成達不足以填充一或多個間隙特徵的厚度(可如同一或多個間隙特徵廣距地隔開並具有高深寬比的情況),且例示性間隙填充製程100可重複一或多次。
更詳細地,例示性間隙填充製程100可包含超循環125,其中超循環可重複一或多次,單位超循環125包含:藉由循環沉積製程來沉積金屬氧化物膜,且後續使金屬氧化物與有機配體蒸氣接觸,並將金屬氧化物膜的至少一部分轉化成多孔材料。超循環125可執行一或多次,直到多孔材料形成達足以填充一或多個間隙特徵的厚度。
圖4A至圖4E繪示當使用例示性間隙填充製程100之多於一個超循環125時,由例示性間隙填充製程100所形成之半導體結構的截面圖。例如,圖4A繪示半導體結構400,其包含基材402,基材包含間隙特徵404,間隙特徵包含寬間隙及高深寬比,其中d表示間隙寬度,且深寬比可大於1:1、大於2:1、大於4:1、大於8:1、大於20:1、大於40:1、大於80:1或大於150:1。在一些實施例中,間隙、溝槽、貫孔、或其他三維特徵(諸如凹腔結構)具有在平面狀表面的頂部處之小於約500 nm、小於約100 nm、小於約70 nm、小於約50 nm、小於約30 nm、小於約20 nm、小於約10 nm、小於約7 nm、小於約5 nm、或甚至小於約4 nm的寬度或開口,以及大於約5 nm、大於約10 nm、大於約20 nm、大於約40 nm、大於約80 nm、大於約200 nm、大於約500 nm、或甚至大於約1000 nm的深度。在一些實施例中,相較於毯覆晶圓,具有間隙、溝槽、貫孔、或其他三維特徵(如凹腔結構)之晶圓(諸如300 mm圖案化矽晶圓)具有大於5、大於10、大於25、大於50、大於100、大於200倍的表面積。圖4B繪示半導體結構405,其包含具有由循環沉積製程120(圖1及圖2)形成於其上之保形金屬氧化物膜406(例如氧化鋅膜)之基材402。
圖4C繪示半導體結構415,其包含基材402及經由製程方塊130(圖1)(亦即,藉由使金屬氧化物與有機配體接觸並將金屬氧化物膜的至少一部分轉化成多孔材料)所形成之多孔材料410。在此非限制性實例中,金屬氧化物膜的整體厚度均轉化成多孔材料,然而,由金屬氧化物膜至多孔材料之轉化所引發之膨脹及相關聯的膜厚度增加卻不足以填充間隙特徵404。
因此,在本揭露之一些實施例中,可重複例示性間隙填充製程100之超循環125(圖1)以便完全填充間隙特徵。例示性間隙填充製程100因此可返回製程方塊120,並可藉由循環沉積製程120來沉積額外的金屬氧化物膜。例如,圖4D繪示半導體結構420,其包含具有設置於其上之多孔材料410之基材402及設置於多孔材料410上方之額外的金屬氧化物膜422。
額外的金屬氧化物膜一經循環沉積,例示性間隙填充製程可經由製程方塊130來繼續,上述方塊包含使額外的金屬氧化物膜與有機配體蒸氣接觸以及將額外的金屬氧化物之至少一部分轉化成多孔材料。例如,圖4E繪示半導體結構425,其包含基材402、多孔材料410、及額外的多孔材料426,其中額外的多孔材料426填充間隙特徵。一或多個間隙特徵一經以多孔材料填充(亦即,形成多孔材料達所欲厚度),例示性間隙填充製程100(圖1)可經由製程方塊150退出,且具有設置於其上之多孔材料的基材可承受進一步的半導體製造製程以製成所欲的半導體裝置結構。
作為本揭露之實施例的一非限制性實例,圖7繪示半導體結構之掃描穿透電子顯微鏡(STEM)影像,結構包括填以根據本揭露之實施例形成之多孔材料的若干間隙特徵。更詳細地,半導體結構700包含矽基材702,其包括具有大約1:1之深寬比的若干間隙特徵704。具有大約6奈米厚度的保形氧化鋅膜係直接沉積在矽基材702上方,且氧化鋅膜隨後係與2-甲基咪唑接觸以將氧化鋅膜轉化成填充間隙特徵704之多孔材料710。在此非限制性實例中,多孔材料包含稱為ZIF-8之金屬有機框架材料。由圖8證實,確認氧化鋅膜完全轉化成ZIF-8,該圖繪示取自具有與ZIF-8匹配的結晶結構之多孔間隙填充材料710的X光繞射(XRD)測量,且並未指示任何餘留氧化鋅的存在。
本揭露之實施例亦可揭示半導體結構及包括金屬有機框架材料之特定半導體結構。因此,本揭露之實施例可包含半導體結構,其包含:基材,其包含非平面狀表面,表面包括一或多個間隙特徵;及金屬有機框架材料,其經設置在一或多個間隙特徵中並填充一或多個間隙特徵。
更詳細地,圖3C繪示半導體結構308,其包含基材302及金屬有機框架材料310,基材具有設置於其上或其中之一或多個間隙特徵304,框架材料經設置在一或多個間隙特徵304中並填充一或多個間隙特徵304。在本揭露之一些實施例中,一或多個間隙特徵304可具有大於2:1的最大深寬比。在本揭露之一些實施例中,一或多個間隙特徵可具有小於5:1的最小深寬比。
在本揭露之一些實施例中,金屬有機框架材料310可包含ZIF-8。在一些實施例中,金屬有機框架材料310係連續且無針孔的。在一些實施例中,金屬有機框架材料310係無縫的,亦即,無一或多個巨型孔洞。在一些實施例中,金屬有機框架材料310可具有小於4.0、或小於3.5、或小於3.0、或小於2.5、或小於2.2、或小於2.0、或小於1.8、或小於1.6、或小於1.5、或甚至小於1.4的介電常數。在一些實施例中,金屬有機框架材料310可具有0.5nm至2.0nm、大於1.0nm、大於2.0nm、大於5.0nm、大於10nm、大於20nm、大於40nm的孔大小、或者從1至100nm、從2至50nm、從2至30nm、或從5至20nm的孔大小。在一些實施例中,金屬有機框架材料310可具有大於100 m2
/g、大於500 m2
/g、大於1000 m2
/g、大於2500 m2
/g、大於5000 m2
/g、大於7500 m2
/g、或大於10000 m2
/g的表面積。在一些實施例中,金屬有機框架材料310可具有低於2.0 g/cm3
、低於1.5 g/cm3
、低於1.5 g/cm3
、低於1.0 g/cm3
、低於0.7 g/cm3
、低於0.5 g/cm3
、低於0.4 g/cm3
、低於0.3 g/cm3
、低於0.2 g/cm3
、低於0.15 g/cm3
的體積質量密度。
上文所述之本揭露之實例實施例並未限制本發明的範疇,因為這些實施例僅為本發明之實施例之實例,本發明之範疇係由隨附之申請專利範圍及其法定等同物定義。任何等效實施例係意欲屬於本發明之範疇內。實際上,除本文中所示及所述者以外,所屬技術領域中具有通常知識者可由本說明書明白本揭露之各種修改(諸如所述元件之替代可用組合)。此類修改及實施例亦意欲落在隨附之申請專利範圍的範疇內。
100:製程流程
110:製程
120:循環沉積製/製程方塊
122:製程方塊
124:製程方塊
125:超循環
126:製程方塊
128:製程方塊
130:製程方塊
140:製程方塊
150:製程方塊
302:基材/特徵
304:特徵
306:金屬氧化物膜
310:材料
306A:側壁
306B:側壁
308:半導體結構
310:材料
302:基材
400:結構
402:基材
404:特徵
405:半導體結構
406:金屬氧化物膜
410:材料
420:半導體結構
422:金屬氧化物膜
425:半導體結構
426:多孔材料
500:半導體結構
502:基材
504:特徵
506:膜
600:半導體結構
602:基材
604:特徵
606:材料
608:縫
700半導體結構
702:基材
704:特徵
710:材料
d:間隙寬度
雖然本說明書以特別指出且明確主張被視為本發明實施例之權利的申請專利範圍作為結論,但是當結合伴隨圖式閱讀時,可從本揭露的實施例之某些實例的描述更容易地探知本揭露之實施例的優點,其中:
圖1繪示根據本揭露之實施例用於填充間隙特徵之非限制性例示性製程流程;
圖2繪示根據本揭露之實施例代表在用於填充間隙特徵的製程中用作子製程之循環沉積製程的非限制性例示性製程;
圖3A至圖3C繪示根據本揭露之實施例藉由間隙填充製程形成之半導體結構的截面示意圖;
圖4A至圖4E繪示根據本揭露之實施例藉由間隙填充製程形成之半導體結構的額外截面示意圖;
圖5繪示根據本揭露之實施例半導體結構的場發射掃描電子顯微鏡(FESEM)影像,該半導體結構包括具有設置於其上之保形金屬氧化物的間隙特徵;
圖6繪示半導體結構的截面圖,半導體結構包括填以介電間隙填充材料的間隙特徵,其包括如先前技術之方法所形成的縫;
圖7繪示根據本揭露之實施例半導體結構之掃描穿透電子顯微鏡(STEM)影像,該半導體結構包括填以多孔材料之若干間隙特徵;及
圖8繪示根據本揭露之實施例取自多孔間隙填充材料之X光繞射(XRD)測量。
無
100:製程流程
110:製程
120:循環沉積製/製程方塊
125:超循環
130:製程方塊
140:製程方塊
150:製程方塊
Claims (21)
- 一種用於填充基材表面上之間隙特徵之方法,該方法包含: 提供一基材,其包含一非平面狀表面,該表面包括一或多個間隙特徵; 藉由一循環沉積製程在該一或多個間隙特徵的一表面上方沉積一Zr或Al氧化物膜; 使該金屬氧化物膜與一有機配體蒸氣接觸;及 將該金屬氧化物膜的至少一部分轉化成一多孔材料,從而填充該一或多個間隙特徵。
- 請求項1所述之方法,其中使該金屬氧化物膜與該有機配體蒸氣接觸及將該金屬氧化物的至少一部分轉化成該多孔材料係同時執行,該金屬氧化物膜與該有機配體蒸氣之該接觸產生該金屬氧化物膜的至少一部分至該多孔材料之該轉化。
- 如請求項1所述之方法,其中該一或多個間隙特徵具有大於2:1的一最大深寬比。
- 如請求項1所述之方法,其中該一或多個間隙特徵具有小於5:1的一最小深寬比。
- 如請求項1所述之方法,其中沉積該金屬氧化物膜進一步包含沉積一保形金屬氧化物膜,其具有大於90%的一步階覆蓋。
- 如請求項1所述之方法,其中該循環沉積製程包含至少一單位循環,一個單位循環包含: 使該基材與一金屬氣相前驅物接觸;及 使該基材與一氧化前驅物接觸。
- 如請求項6所述之方法,其中該金屬氣相前驅物包含選自包含鋯(Zr)或鋁(Al)的群組之一金屬,且其中該氧化前驅物包含水(H2 O)、過氧化氫(H2 O2 )、臭氧(O3 )、一有機醇、或一氧基電漿之至少一者。
- 如請求項1所述之方法,其中該金屬氧化物包含一氧化鋅。
- 如請求項1所述之方法,其中該金屬氧化物膜係沉積達小於20奈米的一厚度。
- 如請求項1所述之方法,其中該有機配體蒸氣包含一羧酸蒸氣。
- 如請求項11所述之方法,其中該羧酸蒸氣包含1,4-苯二羧酸、2,6-萘二羧酸、或1,3,5-苯三羧酸之至少一者的一蒸氣。
- 如請求項1所述之方法,其中該有機配體蒸氣包含一吡咯蒸氣。
- 如請求項13所述之方法,其中該吡咯蒸氣包含2-甲基咪唑、3-(2-吡啶基)-5-(4-吡啶基-1,2,4-三吡咯)、或4,5-二氯咪唑之至少一者的一蒸氣。
- 如請求項1所述之方法,其中該多孔材料包含一金屬有機框架材料。
- 如請求項15所述之方法,其中該金屬有機框架材料具有小於大約4.0的一介電常數。
- 如請求項15所述之方法,其中該金屬有機框架材料係連續且無針孔的。
- 如請求項15所述之方法,其中該金屬有機框架材料具有小於50奈米的一厚度。
- 如請求項1所述之方法,其中該多孔材料填充該一或多個間隙特徵而不形成一縫。
- 如請求項1所述之方法,其中轉化該金屬氧化物膜的至少一部分包含將該金屬氧化物膜完全轉換成該多孔材料。
- 如請求項1所述之方法,其進一步包含重複沉積該金屬氧化物膜及使該金屬氧化物與該有機配體蒸氣接觸之該等步驟一或多次。
- 如請求項1所述之方法,其中該金屬氧化物膜具有一初始厚度,且將該金屬氧化物膜的至少一部分轉化成該多孔材料所產生的該多孔材料在無額外沉積的情況下具有大於該初始厚度的一厚度。
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KR20210117157A (ko) | 2020-03-12 | 2021-09-28 | 에이에스엠 아이피 홀딩 비.브이. | 타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법 |
CN113394067A (zh) | 2020-03-13 | 2021-09-14 | Asm Ip私人控股有限公司 | 基板处理设备 |
US20210292902A1 (en) | 2020-03-17 | 2021-09-23 | Asm Ip Holding B.V. | Method of depositing epitaxial material, structure formed using the method, and system for performing the method |
KR20210124042A (ko) | 2020-04-02 | 2021-10-14 | 에이에스엠 아이피 홀딩 비.브이. | 박막 형성 방법 |
TW202146689A (zh) | 2020-04-03 | 2021-12-16 | 荷蘭商Asm Ip控股公司 | 阻障層形成方法及半導體裝置的製造方法 |
TW202145344A (zh) | 2020-04-08 | 2021-12-01 | 荷蘭商Asm Ip私人控股有限公司 | 用於選擇性蝕刻氧化矽膜之設備及方法 |
KR20210127087A (ko) | 2020-04-10 | 2021-10-21 | 에이에스엠 아이피 홀딩 비.브이. | 기체 공급 유닛 및 이를 포함하는 기판 처리 장치 |
KR20210127620A (ko) | 2020-04-13 | 2021-10-22 | 에이에스엠 아이피 홀딩 비.브이. | 질소 함유 탄소 막을 형성하는 방법 및 이를 수행하기 위한 시스템 |
KR20210128343A (ko) | 2020-04-15 | 2021-10-26 | 에이에스엠 아이피 홀딩 비.브이. | 크롬 나이트라이드 층을 형성하는 방법 및 크롬 나이트라이드 층을 포함하는 구조 |
US11821078B2 (en) | 2020-04-15 | 2023-11-21 | Asm Ip Holding B.V. | Method for forming precoat film and method for forming silicon-containing film |
US20210327704A1 (en) | 2020-04-16 | 2021-10-21 | Asm Ip Holding B.V. | Methods of forming structures including silicon germanium and silicon layers, devices formed using the methods, and systems for performing the methods |
KR20210129598A (ko) | 2020-04-17 | 2021-10-28 | 에이에스엠 아이피 홀딩 비.브이. | 수직형 퍼니스의 반응기 내에 배열되도록 구성된 인젝터와 수직형 퍼니스 |
TW202143328A (zh) | 2020-04-21 | 2021-11-16 | 荷蘭商Asm Ip私人控股有限公司 | 用於調整膜應力之方法 |
-
2020
- 2020-12-07 KR KR1020200169793A patent/KR20210080214A/ko unknown
- 2020-12-07 US US17/113,441 patent/US11527403B2/en active Active
- 2020-12-11 TW TW109143761A patent/TW202129052A/zh unknown
- 2020-12-15 CN CN202011478790.6A patent/CN113013084A/zh active Pending
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2022
- 2022-12-12 US US18/079,160 patent/US20230170207A1/en active Pending
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US11527403B2 (en) | 2022-12-13 |
CN113013084A (zh) | 2021-06-22 |
US20230170207A1 (en) | 2023-06-01 |
KR20210080214A (ko) | 2021-06-30 |
US20210193458A1 (en) | 2021-06-24 |
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