TWI761636B - 電漿增強型原子層沉積製程及沉積碳氧化矽薄膜的方法 - Google Patents
電漿增強型原子層沉積製程及沉積碳氧化矽薄膜的方法 Download PDFInfo
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Abstract
提供在基板的兩個或更多個不同表面上沉積碳氧化矽的
電漿增強型原子層沉積(PEALD)製程。舉例來說,碳氧化矽可同時沉積於第一介電質表面及第二金屬或金屬性表面上。電漿增強型原子層沉積製程可包括兩個或更多個用來於兩表面上形成碳氧化矽的沉積循環。沉積循環可包括使基板交替地及依序地與包含矽的第一前驅物及諸如氬/氫(Ar/H2)電漿的第二電漿反應物接觸。在一些實施例中,電漿增強型原子層沉積製程進一步包括在開始沉積循環的前使基板與電漿反應物接觸。在一些實施例中,將沉積循環重複多於500次且可於兩不同表面上形成均勻的碳氧化矽膜。
Description
本申請案大致是關於碳氧化矽(SiOC)的電漿增強型原子層沉積(plasma enhanced atomic layer deposition;PEALD)。
[相關申請案的交叉參考]本申請案主張2017年12月4日提出申請的美國臨時申請案第62/594,474號的優先權,該案全文以引用的方式併入本文。
在半導體工業中,需以良好均勻性於不同基板表面上沉積低介電常數間隔件(low-K spacer;LKS)。可由不同材料構成這些不同的表面,例如金屬及介電質。於兩種或更多種不同基板表面上均勻沉積一種材料可能是有好處的,例如,藉由此來減少裝置製造中的步驟數。亦有具有低介電常數(k)值及低蝕刻速率的介電材料的需求,例如,在諸如氫氟酸(HF)的酸基蝕刻溶液中。
根據一個態樣,提供一種用來在基板的兩個或更多個不同表面上沉積碳氧化矽(SiOC)的電漿增強型原子層沉積製程。在一些實施例中,電漿增強型原子層沉積製程可包括提供包括第一表面及第二表面的基板,其中第一表面包含不同於第二表面的材料,及於兩表面上進行兩個或更多個用來形成碳氧化矽的沉積循環。沉積循環可包括使基板交替地及依序地與包含矽的第一前驅物及第二電漿反應物接觸。在一些實施例中,電漿增強型原子層沉積製程進一步包括在開始沉積循環之前使基板與電漿反應物接觸。在一些實施例中,重複沉積循環多於500次。在一些實施例中,將碳氧化矽膜均勻地沉積於第一表面及第二表面上。在一些實施例中,碳氧化矽膜具有小於4的介電常數值。
在一些實施例中,第一表面是金屬表面及第二表面是介電質表面。在一些實施例中,介電質表面包括二氧化矽(SiO2)。在一些實施例中,金屬表面包含鎢(W)。
在一些實施例中,第一前驅物是矽前驅物。在一些實施例中,矽前驅物具有化學式Si(ORI)4-xRII x,使得x=0至3,RI是具有1至5個碳的烷基及RII是任何含有碳及/或氫及/或氧的配位基(ligand)且所有的RI及RII基團可獨立地選擇。在一些實施例中,RII具有烯基、炔基、苯基、羰基、醛、酯、醚、羧基、過氧基或氫過氧基的官能基且所有RI及RII基團可彼此獨立地選擇。在一些實施例中,第一前驅物為3-甲氧基丙基三甲氧基矽烷
((3-Mercaptopropyl)trimethoxysilane;MPTMS)。
在一些實施例中,電漿反應物包含氬/氫(Ar/H2)電漿。在一些實施例中,電漿反應物不包含氧物種。
在一些實施例中,第一前驅物是3-甲氧基丙基三甲氧基矽烷及第二反應物包含氬/氫電漿。
在一些實施例中,將碳氧化矽薄膜沉積於基板的第一介電質表面及同一基板的第二金屬表面兩者上的方法包括兩個或更多個沉積循環,其中使基板交替地及依序地與包含矽的第一反應物及不包含氧物種的第二電漿反應物接觸。在一些實施例中,第一反應物是3-甲氧基丙基三甲氧基矽烷及第二反應物是於氬/氫氣體中產生的電漿。在一些實施例中,介電質表面包含二氧化矽及金屬表面包含鎢。
在一些實施例中,描述電漿增強型原子層沉積製程,其用於將碳氧化矽沉積於包含二氧化矽的基板的第一表面及包含鎢的基板的第二表面上。電漿增強型原子層沉積製程可包括兩個或更多個沉積循環,其依序包括以下步驟。使基板與包含3-甲氧基丙基三甲氧基矽烷的第一反應物接觸。使基板與沖洗氣體(purge gas)接觸。使基板與氬/氫電漿接觸。以及,再次使基板與沖洗氣體接觸。在一些實施例中,該製程另包括在第一沉積循環之前使基板與電漿反應物接觸。在一些實施例中,使碳氧化矽均勻地沉積於第一及第二表面上。
圖1是沉積於介電質及金屬表面兩者上的均勻碳氧化矽層的示意圖。
圖2是在200℃及200W下沉積於鎢及二氧化矽圖案上的碳氧化矽膜的掃描穿透電子顯微鏡(STEM)。左圖顯示於1000個沉積循環後的膜。右圖顯示於500個沉積循環後的膜。
圖3顯示在500個沉積循環後沉積於12nm物理氣相沉積的氮化鈦(PVD TiN)金屬性表面上的與3-甲氧基丙基三甲氧基矽烷相關的碳氧化矽的X-射線反射率(X-ray reflectivity;XRR)光譜。
如熟習本領域的技術人員將顯而易見的,碳氧化矽膜例如在積體電路製造中具有廣泛多種應用。在一些態樣中,將碳氧化矽膜沉積於兩個或更多個不同表面,例如,如圖1中所說明的金屬表面及介電質表面上。在一些實施例中,碳氧化矽膜是藉由單一沉積製程沉積於兩個或更多個不同表面上。舉例來說,碳氧化矽膜可藉由電漿增強型原子層沉積製程沉積於基板的兩個不同表面上。在一些態樣中,藉由無氧電漿增強型原子層沉積製程將例如於氫氟酸或稀氫氟酸中具有低蝕刻速率的碳氧化矽膜沉積於包含第一材料的第一表面及包含不同的第二材料的第二表面上。在一些實施例中,製程使用矽-烷氧基類前驅物及電漿,諸如氬/
氫電漿。製程可被控制並於多種不同基板表面上達成均勻的膜沉積。
根據一些實施例,碳氧化矽膜是使用電漿增強型原子層沉積製程來沉積,其包括使基板交替地與第一矽烷氧基前驅物及電漿反應物(諸如氬/氫電漿)接觸。第一前驅物可包含氧及矽兩者。膜生長於第一表面(諸如介電質表面)及第二不同表面(諸如金屬或金屬性表面)上。過量的反應物及/或反應副產物可於接觸步驟之間,以諸如經由將基板暴露至沖洗氣體使過量的反應物及/或反應副產物自基板表面移除。
在一些實施例中,提供包含第一表面(諸如介電質表面)及第二不同表面(諸如金屬表面)的基板。使該基板交替地及依序地與矽前驅物(諸如矽烷氧基前驅物)及電漿反應物(諸如氬/氫電漿)接觸。電漿及矽前驅物可以脈衝(pulse)的形式被提供,並透過沖洗彼此間隔開。若有過量反應物及反應副產物則藉由沖洗自基板表面移除。在一些實施例中,使第一表面及第二表面在矽反應物及電漿的脈衝之間與沖洗氣體接觸。
在一些實施例中,沉積製程始於矽反應物脈衝,且反應順序、或沉積循環可被重複期望的次數(A):A x(矽前驅物脈衝/沖洗/電漿脈衝/沖洗)
在一些實施例中,沉積循環始於電漿脈衝,其後為矽前驅物脈衝。
在一些實施例中,重複沉積循環直至將均勻的碳氧化矽
膜沉積於兩個或更多個不同表面上為止。在一些實施例中,將沉積循環重複至少100次、至少200次、至少300次,至少400次、或至少500次。在一些實施例中,重複沉積循環至少1000次。可重複沉積循環直至已將期望厚度的膜形成於兩個或更多個不同表面上為止。
藉由選擇特定製程條件,諸如反應物的性質、溫度、脈衝及沖洗次數、電漿功率、及沉積循環數,可於兩個或更多個不同表面上達成所期望均勻度的沉積。在一些實施例中,可調整製程條件,諸如電漿功率,使得於兩個或更多個不同表面上均勻地進行生長。
在一些實施例中,當膜於至少第一表面與第二不同表面之間具有變化小於75%、小於50%、小於40%、小於30%、小於20%、小於15%、小於10%、小於9%、小於8%、小於7%、小於6%、小於5%、小於4%、小於3%、小於2%或甚至小於1%的厚度時,將其視為均勻地沉積。在一些實施例中,厚度是經測量為沉積於特定表面上的膜的平均厚度。在一些實施例中,均勻性是經測量為在兩個不同表面間測得的實際厚度變化。
在一些實施例中,電漿反應物是以氫為主。舉例來說,電漿可於氫氣氣體或氫氣及稀有氣體(諸如氬氣)的混合物中產生。在一些實施例中,電漿是於氫氣及氬氣氣體的混合物中產生(稱為氬/氫電漿)。在一些實施例中,電漿不含氧氣。換言的,電漿是在不含氧的氣體或氣體混合物中產生。
在一些實施例中,例如是含氫電漿的電漿可藉由向反應物氣體或氣體混合物施加約5W至約5000W、約10W至約2000W、約50W至約1000W或約100W至約500W的射頻(RF)功率來產生。在一些實施例中,射頻功率密度可約0.02W/cm2至約2.0W/cm2、或約0.05W/cm2至約1.5W/cm2。可將射頻功率施加至在電漿接觸時間期間流動、連續流經反應室、及/或流經遠端電漿產生器的氣體。因此,在一些實施例中,就地(in situ)產生電漿,而在其他實施例中,在遠端產生電漿。在一些實施例中,利用噴淋頭(showerhead)反應器且在晶座(被定位的基板的頂部上)與噴淋頭板的間產生電漿。
在一些實施例中,沉積速率在兩表面上相似。在一些實施例中,沉積速率在兩個或更多個不同表面的間不同。舉例來說,在一些實施例中,在其中一個表面上可能具有相對於另一者長的培養時間(incubation time)。在一些實施例中,在一個表面上的生長速率可能不同於在另一表面上。在一些實施例中,在一或多個表面上的沉積速率可隨時間改變。舉例來說,在一個表面上的沉積速率可能增加,同時在第二表面上的沉積速率維持恆定。
在一些實施例中,可選擇沉積時間以於兩個或更多個不同表面上,諸如於同一基板的介電質表面及金屬表面兩者上,達成相似、相對均勻厚度的碳氧化矽膜的沉積。
在一些實施例中,選擇沉積循環數以於基板的兩個或更多個不同表面上達成相似、相對均勻厚度的碳氧化矽膜的沉積。
在一些實施例中,沉積製程是於低處理溫度下進行。在一些實施例中,沉積溫度是低於約500℃、低於約400℃、低於約300℃、低於約200℃或低於約100℃。在一些實施例中,碳氧化矽膜是在約100℃至約300℃的溫度下沉積。在一些實施例中,碳氧化矽膜是在約150℃至250℃的溫度下沉積。在一些實施例中,碳氧化矽膜是在約200℃的溫度下沉積。
在一些實施例中,碳氧化矽膜是在同一沉積製程中沉積於包含不同材料的兩個或更多個不同表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於包含兩種或更多種不同材料的兩個或更多個不同表面上,例如各包含不同材料的三個或更多個不同表面、各包含不同材料的四個或更多個不同表面等。在一些實施例中,兩個或更多個不同表面是在同一基板上。在一些實施例中,兩個或更多個表面相鄰。
在一些實施例中,碳氧化矽膜是沉積於基板的所有表面上。
在一些實施例中,碳氧化矽膜是沉積於兩個或更多個不同表面上,其中該兩個或更多個不同表面包含,例如,金屬、氧化物、氧化金屬、天然金屬氧化物、天然二氧化矽、矽、介電質、二氧化矽、及/或氮化矽(Si3N4)。
在一些實施例中,碳氧化矽膜是沉積於兩個不同表面上,其中一個表面是介電材料且另一表面包含金屬或金屬性材料。
在一些實施例中,介電質表面可為,例如,二氧化矽表
面或低介電常數表面。在一些實施例中,介電材料包含二氧化矽、一氮化矽(SiN)及多晶矽中的一或多者。在一些實施例中,介電材料是二氧化矽。在一些實施例中,介電材料是一氮化矽。在一些實施例中,介電材料是多晶矽。
在一些實施例中,碳氧化矽膜是沉積於第一表面及包含不同於第一表面的材料的第二表面兩者上。舉例來說,碳氧化矽膜可沉積於第一金屬或金屬性表面及第二介電質表面上。在一些實施例中,碳氧化矽膜是沉積於二氧化矽表面及金屬表面上。在一些實施例中,碳氧化矽膜是沉積於二氧化矽表面及鎢表面上。在一些實施例中,碳氧化矽膜是沉積於二氧化矽表面及氮化鈦表面上。在一些實施例中,碳氧化矽膜是沉積於鎢表面及一氮化矽表面上。在一些實施例中,碳氧化矽膜是沉積於氮化鈦表面及一氮化矽表面上。在一些實施例中,碳氧化矽膜是沉積於鎢表面及多晶矽表面上。在一些實施例中,碳氧化矽膜是沉積於氮化鈦表面及多晶矽表面上。
在一些實施例中,碳氧化矽膜是以良好的均勻性沉積於第一表面及包含不同於第一表面的材料的第二表面兩者上。舉例來說,碳氧化矽膜可同時地及均勻地沉積於第一金屬或金屬性表面及第二介電質表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於二氧化矽表面及金屬表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於二氧化矽表面及鎢表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於二氧化矽表面及氮化鈦表面上。在一
些實施例中,碳氧化矽膜是均勻地沉積於鎢表面及一氮化矽表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於氮化鈦表面及一氮化矽表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於鎢表面及多晶矽表面上。在一些實施例中,碳氧化矽膜是均勻地沉積於氮化鈦表面及多晶矽表面上。
除非另外指定,否則若於本文中將表面稱為金屬表面,其可為金屬表面或金屬性表面。在一些實施例中,金屬或金屬性表面可包含金屬、金屬氧化物、及/或其混合物。在一些實施例中,金屬或金屬性表面可包含表面氧化。在一些實施例中,金屬或金屬性表面的金屬或金屬性材料於存在或不存在表面氧化的情況下具有導電性。在一些實施例中,金屬或金屬性表面包含一或多種過渡金屬。在一些實施例中,金屬或金屬性表面包含鋁(Al)、銅(Cu)、鈷(Co)、鎳(Ni)、鎢、鈮(Nb)、及鐵(Fe)中的一或多者。在一些實施例中,金屬或金屬性表面包含鎢。在一些實施例中,金屬或金屬性表面包含一或多種貴金屬,諸如釕(Ru)。在一些實施例中,金屬或金屬性表面包含一種傳導性金屬氧化物、氮化物、碳化物、硼化物、或其組合。在一些實施例中,基板可包含金屬氮化物,包括但不限於氮化鈦及/或氮化鉭(TaN)。在一些實施例中,金屬表面可包含金屬碳化物。在一些實施例中,金屬表面可包含金屬硫化物。
為方便及簡單起見,氧碳化矽膜的化學式在本文中一般被稱作碳氧化矽。如本文中所使用,碳氧化矽並不意欲限制、侷
限、或界定膜中矽、氧、碳及/或任何其他元素中任一者的鍵結或化學狀態,例如氧化態。此外,在一些實施例中,碳氧化矽薄膜可包含除矽、氧及碳以外外的一或多種元素。
在一些實施例中,碳氧化矽可包含以原子計約0%至約30%碳。在一些實施例中,碳氧化矽膜可包含以原子計約0%至約60%氧。在一些實施例中,碳氧化矽膜可包含以原子計約0%至約50%矽。
在一些實施例中,碳氧化矽膜具有低介電常數值。在一些實施例中,碳氧化矽膜具有小於4的介電常數值。
在一些實施例中,將其上需要沉積的基板(諸如半導體工件)載入至反應空間或反應器中。反應器可為於其中進行積體電路形成中的各種不同製程的群集工具的一部分。在一些實施例中,利用流動型反應器。在一些實施例中,利用噴淋頭型反應器。在一些實施例中,利用空間分割反應器。在一些實施例中,使用能夠進行大量製造的單晶圓原子層沉積反應器。在其他實施例中,使用包含多個基板的分批式(batch)反應器。對於使用分批式原子層沉積反應器的實施例,基板的數目在10至200的範圍內,在50至150的範圍內或在100至130的範圍內。
可使用的合適反應器的實例包括市售設備,諸如可購自亞利桑那州鳳凰城(Phoenix,Arizona)的ASM America,Inc.及荷蘭阿爾梅勒(Almere,Netherlands)的ASM Europe B.V.的F-120®反應器、F-450®反應器、Pulsar®反應器-諸如Pulsar®2000及Pulsar®
3000-EmerALD®反應器及Advance® 400系列反應器。其他市售反應器包括來自ASM Japan K.K(日本東京)商品名為Eagle® XP及XP8的這些反應器。
在一些實施例中,若有需要或期望,可預處理基板的一或多個被暴露的表面以提供與電漿增強型原子層沉積製程的第一階段反應的反應性部位。在一些實施例中,不需要個別的預處理步驟。在一些實施例中,預處理基板以提供期望的表面終止。在一些實施例中,利用電漿預處理基板的一或多個表面。在一些實施例中,利用電漿(例如利用H電漿)預處理欲於其上沉積碳氧化矽的兩個或更多個表面。
在一些實施例中,使金屬或金屬性表面在沉積前受到表面處理。舉例來說,可藉由暴露於電漿來處理金屬或金屬性表面。在一些實施例中,金屬或金屬性表面可在沉積前利用H電漿處理。在一些實施例中,在沉積前利用H電漿處理鎢表面。
在一些實施例中,使基板與第一矽前驅物及第二電漿反應物接觸。在一些實施例中,沉積製程不含鹵素。在一些實施例中,沉積製程不含氧。
在一些實施例中,矽前驅物具有化學式(1.):Si(ORI)4-xRII x
其中x=0至3,RI是具有1至5個碳的烷基及RII是任何含有碳及/或氫及/或氧的配位基。RII可具有,例如,烯基、炔基、苯基、羰基、醛、酯、醚、羧基、過氧基或氫過氧基官能性。
所有RI及RII基團可彼此獨立地選擇。
在一些實施例中,矽前驅物為3-甲氧基丙基三甲氧基矽烷。在實例化合物3-甲氧基丙基三甲氧基矽烷中,RI是甲基,RII是3-甲氧丙基,及x是1。
如前文所述,在一些實施例中,電漿增強型原子層沉積製程不包含氧電漿或含氧物種的電漿。
在一些實施例中,為形成碳氧化矽膜,每一電漿增強型原子層沉積循環包含至少兩個相異階段。可將反應物與基板的接觸及自基板移除反應物視為一階段。
在第一階段中,包含矽的氣相第一反應物接觸基板並於期望沉積的表面上形成不超過約一個單層。此反應物在本文中亦被稱作「矽前驅物」、「含矽前驅物」或「矽反應物」,且可以是例如3-甲氧基丙基三甲氧基矽烷。在一些實施例中,第一反應物同時包含矽及氧。
在第二階段中,包含反應性物種的第二反應物接觸基板表面且可於介電質表面上將被吸附的矽轉變為碳氧化矽。如前文所論述,在一些實施例中,第二反應物包含氫電漿,諸如氫氣/氬氣電漿。
在一些實施例中,用來形成電漿的氣體可在整個沉積製程中恆定地流動,但僅間歇地被啟動。
在一些實施例中,用來形成電漿的氣體不包含氧。在一些實施例中,所吸附的矽前驅物不與由來自氧氣的電漿產生的反
應性物種接觸。在一些實施例中,於不包含氧的氣體中產生包含反應性物種的第二反應物。舉例而言,在一些實施例中,第二反應物可包含在不包含氧氣的氣體中產生的電漿。在一些實施例中,可於包含少於約1原子百分比(at%)的氧、少於約0.1原子百分比的氧、少於約0.01原子百分比的氧、或少於約0.001原子百分比的氧的氣體中產生第二反應物。
可視需要添加額外階段且可移除階段來調整最終膜的組成。
在一些實施例中,為沉積碳氧化矽膜,一或多個沉積循環始於使基板與矽前驅物接觸,隨後再與第二電漿反應物接觸。在其他實施例中,沉積可始於使基板與第二電漿反應物接觸,隨後再與矽前驅物接觸。
在反應物接觸階段之間,自基板附近且尤其自基板表面移除過量的反應物及反應副產物(若存在)。在一些實施例中,過量的反應物及反應副產物(若存在)是藉由例如在反應物接觸階段之間沖洗反應室,諸如藉由利用惰性氣體沖洗而自基板表面移除。每一反應物的流動速率及接觸時間是可調整的,正如移除步驟一樣,從而允許控制膜的品質及各種性質。
沉積循環是經重複直至於期望表面上獲得期望厚度的碳氧化矽膜為止。在一些實施例中,可在電漿增強型原子層沉積製程期間於一或多個沉積循環中改變沉積參數,諸如前驅物流動速率、接觸時間、移除時間、及/或反應物本身,以於兩個或更多個
不同表面上獲得具有期望特性的膜。
在一些實施例中,第二電漿反應物是在兩個或多於兩個相異的脈衝中被提供,而不在兩個或多於兩個脈衝中的任何一者的間引入另一反應物。舉例而言,在一些實施例中,電漿是在兩個或多於兩個依序的脈衝中被提供,而不在依序的電漿脈衝之間引入矽前驅物。在一些實施例中,在提供電漿期間,藉由以下步驟產生兩個或多於兩個依序的電漿脈衝。提供電漿放電持續第一時間段。熄滅電漿放電持續第二時間段,例如約0.1秒至約10秒、約0.5秒至約5秒或約1.0秒至約4.0秒。以及,再次激發電漿放電持續第三時間段,隨後引入另一前驅物或移除步驟,諸如隨後引入矽前驅物或沖洗步驟。額外的電漿脈衝可以同一方式引入。在一些實施例中,在這些脈衝的每一者中,電漿點火持續相等的時間段。
在一些實施例中,移除過量的反應物及反應副產物(若存在),可包含沖洗反應室。在一些實施例中,可藉由停止第二反應物的流動,同時使載氣(carrier gas)或沖洗氣體繼續流動足夠的時間,以使過量的反應物及反應副產物(若存在)自反應空間擴散或排出來沖洗反應室。在一些實施例中,過量的第二前驅物是藉助在整個電漿增強型原子層沉積循環中流動的諸如氮或氬的惰性氣體來沖洗。在一些實施例中,可將基板自含有第二反應物的反應空間移動至不同的反應空間。在一些實施例中,移除可持續約0.1秒至約10秒、約0.1秒至約4秒或約0.1秒至約0.5秒。反應性物
種接觸及移除一起表示為碳氧化矽原子層沉積循環中的第二反應性物種階段。
根據本發明的一些實施例,在處理期間反應室的壓力維持在約0.01托(Torr)至約50托、或約0.1托至約10托。在一些實施例中,反應室的壓力大於約6托或約20托。
根據一些實施例,碳氧化矽薄膜是在反應空間中藉由包括至少一個循環的電漿增強型原子層沉積沉積製程沉積於基板的兩個或多於兩個不同表面上,該循環包括以下步驟。
使基板與矽反應物接觸,以使矽物種吸附於基板表面上。
若有過量的矽反應物及反應副產物,自基板表面移除。
使基板與包含由電漿產生的反應性物種的第二反應物接觸。
若有過量的第二反應物及反應副產物,自基板表面移除。
以及,視情況重複接觸及移除步驟,以於兩個或多於兩個不同表面上形成所期望的厚度及組成的碳氧化矽薄膜。
實施例
使用直接電漿電漿增強型原子層沉積反應器,藉由電漿增強型原子層沉積使用3-甲氧基丙基三甲氧基矽烷作為矽前驅物來沉積碳氧化矽膜。由於化合物的足夠高的蒸氣壓,不需要加熱前驅物來產生氣相反應物。在200℃的沉積溫度下進行實驗。製程的每個循環的生長速率(growth rate per cycle;GPC)通常是大約0.2Å/c。圖2顯示在200℃下於包含鎢及二氧化矽的相鄰水平表
面的基板上沉積的碳氧化矽膜的掃描電子顯微鏡(SEM)影像。
如圖2的右圖所示,於500個循環後,碳氧化矽膜沉積於二氧化矽表面上,同時於相鄰鎢表面上幾乎未觀察到沉積。然而,如圖2的左圖所示,於較長的沉積時間,明確言為1000個循環後,碳氧化矽於鎢及二氧化矽表面兩者上沉積至相似程度。雖然可於鎢及二氧化矽表面的間觀察到碳氧化矽層的厚度的一些差異,但預期厚度差異會隨再更長的沉積而減少。觀察到的結果指出鎢表面上的碳氧化矽沉積相較於二氧化矽表面上有更長的培養時間。
圖3顯示使用3-甲氧基丙基三甲氧基矽烷作為矽前驅物於500個循環後將約6.2nm的碳氧化矽膜沉積於氮化鈦表面上,其指出相較於天然氧化物表面上所觀察到的碳氧化矽膜的每個循環的生長,使用3-甲氧基丙基三甲氧基矽烷作為矽前驅物於500個循環後將約6.2nm的碳氧化矽膜沉積於氮化鈦表面上的每個循環的生長稍低。
Claims (20)
- 一種電漿增強型原子層沉積(PEALD)製程,其用於將碳氧化矽(SiOC)沉積於基板的兩個或更多個不同表面上,包括:提供包括第一表面及第二表面的基板,其中該第一表面包含不同於該第二表面的材料,其中該第一表面是金屬表面及該第二表面是介電質表面;進行兩個或更多個沉積循環,該些沉積循環包括使該基板的該第一表面及該第二表面交替地及依序地與包含矽的第一前驅物及第二電漿反應物接觸。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該介電質表面包含二氧化矽。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該金屬表面包含鎢。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該第二電漿反應物包含氬/氫電漿。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該第二電漿反應物不包含氧物種。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該第一前驅物是矽前驅物。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該第一前驅物具有化學式Si(ORI)4-xRII x,其中x=0至3,RI是具有1至5個碳的烷基及RII是任何含有碳及/或 氫及/或氧的配位基,且所有的RI及RII基團可獨立地選擇。
- 如申請專利範圍第7項所述的電漿增強型原子層沉積製程,其中RII具有烯基、炔基、苯基、羰基、醛、酯、醚、羧基、過氧基或氫過氧基的官能基,且其中所有RI及RII基團可彼此獨立地選擇。
- 如申請專利範圍第7項所述的電漿增強型原子層沉積(PEALD)製程,其中該第一前驅物是3-甲氧基丙基三甲氧基矽烷。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該第一前驅物是3-甲氧基丙基三甲氧基矽烷(MPTMS)及該第二電漿反應物包含氬/氫(Ar/H2)電漿。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,另外包括在開始該沉積循環之前使該基板與電漿反應物接觸。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該碳氧化矽均勻地被沉積於該第一表面及該第二表面上。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中重複該沉積循環多於500次。
- 如申請專利範圍第1項所述的電漿增強型原子層沉積(PEALD)製程,其中該碳氧化矽形成具有小於4的介電常數(k)值的膜。
- 一種沉積碳氧化矽薄膜的方法,其將碳氧化矽薄膜沉 積於基板的第一介電質表面及同一該基板的第二金屬表面兩者上,包括:兩個或更多個沉積循環,該些沉積循環包括使該基板交替地及依序地與包含矽的第一反應物及不包含氧物種的第二電漿反應物接觸。
- 如申請專利範圍第15項所述的方法,其中該第一反應物是3-甲氧基丙基三甲氧基矽烷及該第二電漿反應物是於氬/氫氣體中產生的電漿。
- 如申請專利範圍第15項所述的方法,其中該第一介電質表面包含二氧化矽及該第二金屬表面包含鎢。
- 一種電漿增強型原子層沉積製程,其用於將碳氧化矽沉積於包含二氧化矽的基板的第一表面及包含鎢的該基板的第二表面上,包括:兩個或更多個沉積循環,該些沉積循環依序包括:使該基板與包含3-甲氧基丙基三甲氧基矽烷的第一反應物接觸;使該基板與沖洗氣體接觸;使該基板與氬/氫電漿接觸;以及使該基板與沖洗氣體接觸。
- 如申請專利範圍第18項所述的電漿增強型原子層沉積製程,另外包括在第一個沉積循環之前使該基板與電漿反應物接觸。
- 如申請專利範圍第18項所述的電漿增強型原子層沉積製程,其中該碳氧化矽均勻地被沉積於該第一表面及該第二表面上。
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