TW201316407A - 用於半導體處理之流動性矽碳氮層 - Google Patents
用於半導體處理之流動性矽碳氮層 Download PDFInfo
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- TW201316407A TW201316407A TW101132769A TW101132769A TW201316407A TW 201316407 A TW201316407 A TW 201316407A TW 101132769 A TW101132769 A TW 101132769A TW 101132769 A TW101132769 A TW 101132769A TW 201316407 A TW201316407 A TW 201316407A
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- nitrogen
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 15
- 238000012545 processing Methods 0.000 title claims description 53
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- -1 1,3,5-trisilapentane (1,3,5-trisilapentane) Chemical compound 0.000 claims description 6
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- PLZDDPSCZHRBOY-UHFFFAOYSA-N 3-methylnonane Chemical compound CCCCCCC(C)CC PLZDDPSCZHRBOY-UHFFFAOYSA-N 0.000 claims 4
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- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
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Abstract
對在半導體基板上形成介電層之方法進行了描述。該方法可包括提供含矽前驅物及高能化(energized)含氮前驅物至化學氣相沉積室,該含矽前驅物與該高能化含氮前驅物可於該化學氣相沉積室中反應,而於該基板上沉積流動性矽碳氮材料。該方法可進一步包括處理該流動性矽碳氮材料,以於該半導體基板上形成該介電層。
Description
本專利申請案主張於2011年9月19日提出申請、標題為「用於半導體處理之流動性含矽碳層(FLOWABLE SILICON-AND-CARBON-CONTAINING LAYERS FOR SEMICONDUCTOR PROCESSING)」的美國臨時專利申請案第61/536,380號的優先權權益。本專利申請案亦主張Mallick等人於2011年9月9日提出申請、標題為「用於半導體處理之流動性矽碳氮層(FLOWABLE SILICON-CARBON-NITROGEN LAYERS FOR SEMICONDUCTOR PROCESSING)」的美國臨時專利申請案第61/532,708號的優先權權益。本專利申請案亦主張Underwood等人於2011年10月24日提出申請、標題為「在沉積流動性含矽碳氮層之後用於降低蝕刻速度之處理(TREATMENTS FOR DECREASING ETCH RATES AFTER FLOWABLE DEPOSITION OF SILICON-CARBON-AND-NITROGEN-CONTAINING LAYERS)」的美國臨時專利申請案第61/550,755號的優先權權益。本專利申請案亦主張Underwood等人於2011年12月7日提出申請、標題為「介電層之摻雜(DOPING OF DIELECTRIC LAYERS)」的美國臨時專利申請案第61/567,738號的優先權權益。為了所有的目的,將以上每一件美國臨時專利申請案之內容全部併入本文中。
本發明係關於半導體處理技術。
半導體電路元件的小型化已經到達了以商業規模製造45 nm、32 nm,甚至是28 nm的特徵尺寸之時間點,隨著尺寸不斷變小,看似平凡的製程步驟也產生了新的挑戰,像是將作為電絕緣的介電材料填充於電路元件之間的縫隙。由於元件之間的寬度不斷縮小,該等元件之間的縫隙時常會變得更高、更窄,使得填充縫隙時介電材料沒有被卡住而產生孔隙和弱接縫是很難的。現有的化學氣相沉積(CVD)技術經常遭遇在完全填滿縫隙之前材料即在縫隙頂部增生,此舉會在縫隙中產生孔隙或接縫,使得沉積的介電材料被該增生過早地切斷,是一個有時也稱作「麵包塊化(breadloafing)」的問題。
麵包塊化問題的現有解決方案是使用液體前驅物作為介電質起始材料,介電質起始材料更容易被注入縫隙中,就像將水裝入玻璃杯一樣,目前在商業使用中如此做的一種技術被稱為旋塗式玻璃(SOG),並採用液體前驅物,該液體前驅物通常是有機矽化合物,而且將有機矽化合物旋轉塗佈於晶圓基板的表面上。雖然液體前驅物的麵包塊化問題較少,但是當前驅物材料轉化為介電
材料時會出現其他的問題。該等轉化時常涉及將沉積的前驅物曝露於分出與趕出該材料中的碳基團之條件下,通常是藉由使該等碳基團與氧反應而產生從該縫隙逸出的一氧化碳與二氧化碳氣體。該等逸出氣體會在介電材料中留下氣孔和氣泡,類似於逸出的二氧化碳在烘烤麵包中留下孔洞。留在最終介電材料中的增大孔隙率會有與現有的CVD技術產生的孔隙和弱接縫相同的有害影響。
近來,賦予CVD沉積的介電材料流動性特性的技術已被開發。該等技術可以沉積流動性前驅物來填充又高又窄的縫隙,而且不會產生孔隙或弱接縫,同時也避免排出顯著量的、會留下氣孔和氣泡的二氧化碳、水及其他物種的氣體之需要。示例性的流動性CVD技術已經使用無碳的矽前驅物,無碳的矽前驅物被沉積在縫隙中之後很少需要去除碳。
雖然新的流動性CVD技術表示將介電材料(如氧化矽)填充於又高又窄的(即高深寬比的)縫隙之重大突破,但仍然需要可以將富含碳的低介電常數(κ)介電材料無縫地填充於該等縫隙之技術。該等材料通常具有比純的氧化矽或氮化物更低的介電常數(κ),並且該等材料通常藉由結合矽與碳物種來實現該等較低的κ水平。除了其他主題之外,本申請案藉由描述用於在基板上形成含矽碳介電材料之流動性CVD技術而解決了該需要。
對在半導體基板上形成及硬化流動性矽碳氮(Si-C-N)層之方法進行了描述。矽與碳組分可來自含矽碳前驅物,而氮可來自已活化的含氮前驅物,以加速氮與含矽碳前驅物於較低的沉積室溫度下之反應。示例性的前驅物包括1,3,5-三矽戊烷(H3Si-CH2-SiH2-CH2-SiH3)作為含矽碳前驅物及電漿活化氨(NH3)作為含氮前驅物。可使用1,4,7-三矽庚烷來取代或加強1,3,5-三矽戊烷。該等前驅物在沉積室中反應時會在半導體基板上沉積流動性Si-C-N層。在基板上那些以高深寬比的縫隙建構的部分中,該流動性Si-C-N材料可被沉積進入該等縫隙中,並且具有明顯較少的孔隙與弱接縫。
初始沉積的流動性Si-C-N可包括顯著數量的Si-H與C-H鍵結,該等鍵結可與空氣中的濕氣和氧以及各種蝕刻劑反應,而造成薄膜加速老化與污染以及蝕刻劑有更高的濕蝕刻速度比(WERR)。在沉積之後,可將Si-C-N薄膜硬化,以減少最終薄膜中Si-H鍵結的數量,同時也增加最終薄膜中Si-Si、Si-C及/或Si-N鍵結的數量。該硬化亦可減少最終薄膜中C-H鍵結的數量並增加C-N及/或C-C鍵結的數量。硬化技術包括使流動性Si-C-N薄膜曝露於電漿,如誘導式耦合電漿(例如高密度電漿化學氣相沉積(HDP-CVD)電漿)或電容式耦合電漿(例如電漿增強化學氣相沉積(PE-CVD)電漿)。在某些實
施例中,沉積室可配備有原位電漿產生系統,以在沉積之後進行電漿處理而不需將基板從該沉積室移出。或者,可將基板轉移至同一製造系統中的電漿處理單元,而不需破真空及/或從該系統移出基板,以允許初始沉積的Si-C-N薄膜可在曝露於來自空氣的濕氣和氧之前進行硬化步驟。
最終的Si-C-N薄膜對於現有的氧化物與氮化物介電質蝕刻劑可皆展現增強的蝕刻抗性。舉例來說,Si-C-N薄膜對於稀釋的氫氟酸溶液(DHF)可以比氧化矽薄膜具有較好的蝕刻抗性,而且Si-C-N薄膜對於熱磷酸溶液也可以比氮化矽薄膜具有較好的蝕刻抗性。對於現有的氧化物與氮化物蝕刻劑皆增強的蝕刻抗性允許該等Si-C-N薄膜在製程常序的過程中保持不受損傷,該製程常序會使基板曝露於該二種類型的蝕刻劑中。
本發明的實施例包括於半導體基板上形成介電層之方法,該方法可包括提供含矽前驅物及高能化含氮前驅物至化學氣相沉積室之步驟,使該含矽前驅物與該高能化含氮前驅物可於該沉積室中反應,而於該基板上沉積流動性矽碳氮材料。該方法可進一步包括處理該流動性矽碳氮材料以於該半導體基板上形成該介電層。
本發明的實施例可進一步包括處理流動性矽碳氮層以降低該層之濕蝕刻速度比(WERR)的方法,該方法可包含藉由含矽前驅物與活化氮前驅物之化學氣相沉積而在基板上形成該流動性矽碳氮層。該方法可進一步包括使該
流動性矽碳氮層曝露於電漿,其中該電漿曝露減少該層中Si-H鍵結之數量並增加該層中Si-C鍵結之數量,以及其中該電漿曝露降低該層之WERR。
在以下的部分描述中提出另外的實施例與特徵,而且對於本技術領域中具有通常知識者而言,在檢視本說明書之後其中的部分將變得顯而易見,或者是可藉由實施本發明而學習其中的部分。藉由說明書中描述的手段、組合以及方法可實現及獲得本發明之特徵與優點。
對應用流動性CVD技術來形成流動性含矽碳氮的材料之方法進行了描述。可以進一步處理該等流動性Si-C-N薄膜,以形成可用於製造積體電路的Si-C-N毯覆層、縫隙填充以及犧牲性阻障層(還有其他元件)。
現在參照第1圖,在基板上形成含矽碳氮的介電層之方法中的精選步驟。該方法可包括提供含矽前驅物至化學氣相沉積室的步驟102。含矽前驅物可提供矽組分給沉積的Si-C-N薄膜,而且含矽前驅物也可提供碳成分。示例性的含矽前驅物除了其他之外包括1,3,5-三矽戊烷(1,3,5-trisilapentane)、1,4,7-三矽庚烷(1,4,7-trisilaheptane)、二矽環丁烷
(disilacyclobutane)、三矽環己烷(trisilacyclohexane)、3-甲基矽烷(3-methylsilane)、矽環戊烯(silacyclopentene)、矽環丁烷(silacyclobutane)以及三甲基矽基乙炔(trimethylsilylacetylene):
另外的示例性含矽前驅物可包括單-、二-、三-、四-及五-矽烷,其中一或多個中央矽原子被氫及/或飽和及/或不飽和烷基基團環繞。該等前驅物之實例可包括SiR4、Si2R6、Si3R8、Si4R10及Si5R12,其中每個R基團係獨立為氫(-H)或飽和或不飽和烷基基團。該等前驅物之特定實例可非限制性地包括以下結構;
更多的示例性含矽前驅物可包括具有式R3Si-[CR2]x-SiR3的二矽烷,其中每個R係獨立為氫(-H)、烷基基團(例如-CH3、-CmH2m+2,其中m為1至10之數)、不飽和烷基基團(例如-CH=CH2)以及其中x為0至10之數。示例性的矽前驅物亦可包括具有式R3Si-[CR2]x-SiR2-[CR2]y-SiR3的三矽烷,其中每個R係獨立為氫(-H)、烷基基團(例如-CH3、-CmH2m+2,其中m為1至10之數)、不飽和烷基基團(例如-CH=CH2)以及其中x與y係獨立為0至10之數。示例性的含矽前驅物可進一步包括具有R3Si-[CH2]n-[SiR3]m-[CH2]n-SiR3形式的矽基烷(silylalkane)與矽基烯(silylalkene),其中
n與m可獨立為1至10之整數,以及每個R基團係獨立為氫(-H)、甲基(-CH3)、乙基(-CH2CH3)、乙烯(-CHCH2)、丙基(-CH2CH2CH3)、異丙基(-CHCH3CH3)等。
示例性的含矽前驅物可進一步包括聚矽基烷化合物,且亦可包括具有複數個矽原子的化合物,該等化合物係選自具有式R-[(CR2)x-(SiR2)y-(CR2)z]n-R的化合物,其中每個R係獨立為氫(-H)、烷基基團(例如-CH3、-CmH2m+2,其中m為1至10之數)、不飽和烷基基團(例如-CH=CH2)或矽烷基團(例如-SiH3,-(Si2H2)m-SiH3,其中m為1至10之數)以及其中x、y及z係獨立為0至10之數,且n為0至10之數。在揭示的實施例中,x、y及z係獨立為介於1與10之間且包含1與10的整數。在本發明之實施例中x與z係相等,且在某些實施例中不管x與z是否相等,y可等於1。在某些實施例中n可為1。
對於兩個R基團皆為-SiH3的實例,該化合物將包括具有式H3Si-[(CH2)x-(SiH2)y-(CH2)z]n-SiH3的聚矽基烷。含矽化合物也可包括具有式R-[(CR' 2)x-(SiR" 2)y-(CR' 2)z]n-R的化合物,其中每個R、R'及R"係獨立為氫(-H)、烷基基團(例如-CH3、-CmH2m+2,其中m為1至10的數)、不飽和烷基基團(例如-CH=CH2)、矽烷基團(例如-SiH3、-(Si2H2)m-SiH3,其中m為1至10的數)以及其中x、y及z係獨立為0至10的數,而且n為0至10的數。在某些實例中,R'
基團及/或R"基團中之一或多個基團可具有式-[(CH2)x-(SiH2)y-(CH2)z]n-R''',其中R'''為氫(-H)、烷基基團(例如-CH3、-CmH2m+2,其中m為1至10的數)、不飽和烷基基團(例如-CH=CH2)或矽烷基團(例如-SiH3、-(Si2H2)m-SiH3,其中m為1至10的數))以及其中x、y及z係獨立為0至10的數,而且n為0至10的數。
還有更多的示例性含矽前驅物可包括矽基烷與矽基烯,如R3Si-[CH2]n-SiR3,其中n可為1至10的整數,而且每個R基團係獨立為氫(-H)、甲基(-CH3)、乙基(-CH2CH3)、乙烯(-CHCH2)、丙基(-CH2CH2CH3)、異丙基(-CHCH3CH3)等。該含矽前驅物亦可包括矽環丙烷(silacyclopropanes)、矽環丁烷(silacyclobutanes)、矽環戊烷(silacyclopentanes)、矽環己烷(silacyclohexanes)、矽環庚烷(silacycloheptanes)、矽環辛烷(silacyclooctanes)、矽環壬烷(silacyclononanes)、矽環丙烯(silacyclopropenes)、矽環丁烯(silacyclobutenes)、矽環戊烯(silacyclopentenes)、矽環己烯(silacyclohexenes)、矽環庚烯(silacycloheptenes)、矽環辛烯(silacyclooctenes)、矽環壬烯(silacyclononenes)等。該等前驅物的特定實例可非限制性地包括以下結構:
示例性的含矽前驅物可進一步包括一或多個與中央碳原子或部分連結的矽烷基團,該等示例性前驅物可包括具有式H4-x-yCXy(SiR3)x的化合物,其中x為1、2、3或4,y為0、1、2或3,每個X係獨立為氫或鹵素(例如F、Cl、Br),而且每個R係獨立為氫(-H)或烷基基團。示例性的前驅物可進一步包括其中中央碳部分為C2-C6飽和或不飽和烷基基團如(SiR3)xC=C(SiR3)x的化合物,其中x為1或2,而且每個R係獨立為氫(-H)或烷基基團。該等前驅物之特定實例可非限制性地包括以下結構:
其中X可為氫或鹵素(例如F、Cl、Br)。
該含矽前驅物亦可包括氮部分。舉例來說,該前驅物可包括經取代或未經取代的Si-N與N-Si-N部分。舉例來說,該前驅物可包括與一或多個氮部分鍵結的中央Si原子,可以式R4-xSi(NR2)x表示,其中x可為1、2、3或4,而且每個R係獨立為氫(-H)或烷基基團。另外的前驅物可包括與一或多個含Si部分鍵結的中央N原子,可以式R4-yN(SiR3)y表示,其中y可為1、2或3,而且每個R係獨立為氫(-H)或烷基基團。進一步的實例可包括具有整合入環結構的Si-N與Si-N-Si基團之環狀化合物。舉例來說,該環結構可具有三個(例如環丙基)、四個(例如環丁基)、五個(例如環戊基)、六個(例如環
己基)、七個(例如環庚基)、八個(例如環辛基)、九個(例如環壬基)或更多的矽與氮原子。在環中的每個原子可與一或多個懸垂部分如氫(-H)、烷基基團(例如-CH3)、矽烷(例如-SiR3)、胺(-NR2)還有其他的基團鍵結。該等前驅物之特定實例可非限制性地包括以下結構:
在期望形成具有低(或無)氧濃度的Si-C-N薄膜之實施例中,可選擇矽前驅物為無氧前驅物,該無氧前驅物不含氧部分。在該等實例中,不會使用現有的如四乙氧基矽烷(TEOS)或四甲氧基矽烷(TMOS)之矽CVD前驅物
作為含矽前驅物。
另外的實施例亦可包括使用無碳矽源,如矽烷(SiH4)及矽基胺(例如N(SiH3)3),還有其他的矽源。碳源可來自分開的前驅物,該分開的前驅物可被獨立提供至沉積室,或是與含矽前驅物混合。示例性的含碳前驅物可包括有機矽烷前驅物及碳氫化合物(例如甲烷、乙烷等)。在某些實例中,含矽碳的前驅物可與無碳的矽前驅物組合,以調整沉積薄膜中的矽碳比率。
除了含矽前驅物之外,還有可將高能化的含氮前驅物加入沉積室中之步驟104。高能化的含氮前驅物可對沉積Si-C-N薄膜貢獻一些或全部的氮組分。使含氮前驅物流入遠端電漿以形成電漿流出物,亦稱為高能化的含氮前驅物。示例性的含氮前驅物之來源可包括氨(NH3)、聯氨(N2H4)、胺、NO、N2O及NO2,還有其他的來源。含氮前驅物可伴隨一或多種另外的氣體,如氫(H2)、氮(N2)、氦、氖、氬等。含氮前驅物亦可含有碳,該碳提供了沉積的Si-C-N層中至少一些的碳組分。示例性的亦含有碳的氮前驅物包括烷基胺。在某些實例中,該另外的氣體亦可至少部分地被電漿解離及/或激化,同時在其他的實例中,該另外的氣體可作為稀釋劑/載體氣體。
含氮前驅物可被電漿高能化,該電漿係於遠端電漿系統(RPS)中形成,遠端電漿系統係位於沉積室外部。當將含氮來源解離、激化及/或以其他方式轉變成高能化含氮前驅物時,可將含氮來源曝露於遠端電漿中。舉例來說,
當含氮前驅物之來源為NH3時,高能化含氮前驅物可包括一或多個.N、.NH、.NH2、氮自由基。然後將高能化的前驅物導入沉積室,在沉積室中高能化的前驅物可首次與獨立導入的含矽前驅物混合。
或者(或另外地),含氮前驅物可在沉積室內部的電漿區中被高能化,該電漿區可與沉積區分隔開,在沉積區該等前驅物混合反應而沉積流動性Si-C-N薄膜於基板的曝露表面上。在該等實例中,可將沉積區描述為在沉積製程的過程中「無電漿」的區域。應注意到,「無電漿」未必是意謂沒有電漿的區域。在腔室的電漿區中很難界定電漿的邊緣,而且電漿的邊緣可能會超出沉積區,例如假使使用噴頭來將前驅物傳送至沉積區時可能會經由噴頭的孔洞傳出沉積區。假使將誘導式耦合電漿整合於沉積室內,則在沉積的過程中可能會在沉積區中啟動少量的離子化。
一旦在沉積室中,高能化的含氮前驅物與含矽前驅物會產生反應(步驟106)而在基板上形成流動性Si-C-N層。在沉積Si-C-N薄膜的過程中,沉積室之反應區中的溫度可以是低的(例如小於100℃),而且腔室總壓可為約0.1 Torr至約10 Torr(例如約0.5至約6 Torr等)。可以部分藉由支撐基板的溫控臺座來控制溫度,該臺座可與冷卻/加熱單元熱耦接,該冷卻/加熱單元將該臺座與基板的溫度調整至例如約0℃至約150℃。
可將初始流動性Si-C-N層沉積於曝露的平面上以及進
入縫隙內。沉積厚度可為約50 Å或更多(例如約100 Å、約150 Å、約200 Å、約250 Å、約300 Å、約350 Å、約400 Å等)。最終的Si-C-N層可為二層或更多的沉積Si-C-N層之累積,該沉積Si-C-N層在沉積後續層之前已經歷處理步驟。舉例來說,該Si-C-N層可為1200 Å厚的層,該1200 Å厚的層係由四層沉積的與處理過的300 Å的層所組成。
初始沉積的Si-C-N層之可流動性可來自由高能化含氮前驅物與含矽碳前驅物混合所產生的各種性質,該等性質可包括在初始沉積的Si-C-N層中的大量氫成分以及短鍊聚矽氮烷聚合物的存在。該可流動性不是依賴高的基板溫度,因此,初始流動性含矽碳氮層可填充縫隙,即使是在相對低溫的基板上。在本發明的實施例中,在形成含矽碳氮層的過程中,基板溫度可低於或約為400℃、基板溫度可低於或約為300℃、基板溫度可低於或約為200℃、基板溫度可低於或約為150℃或是基板溫度可低於或約為100℃。
當流動性Si-C-N層達到所需厚度時,可從沉積室移出製程流出物。該等製程流出物可包括任何未反應的含氮與含矽前驅物、稀釋劑及/或載體氣體,以及未沉積於基板上的反應產物。可藉由排空沉積室及/或以沉積區中的非沉積氣體置換流出物來移出該等製程流出物。
在初始沉積Si-C-N層及選擇性移出該等製程流出物之後,可進行處理步驟108來減少Si-C-N層中的Si-H及/
或C-H鍵結數量,同時亦增加Si-Si、Si-C、Si-N及/或C-N鍵結的數量。如上所指明的,在沉積之後會需要減少該等鍵結的數量,以硬化該層並增加該層對抗蝕刻、老化及污染還有其他形式的層退化之抗性。處理技術可包括使初始沉積的層曝露於一或多種處理氣體(如氦、氮、氬等)之電漿。
該電漿可以是在沉積室的沉積區中原位產生的電容式耦合電漿或誘導式耦合電漿。舉例來說,誘導式耦合電漿處理可在高密度電漿化學氣相沉積(HDP-CVD)沉積室中進行,而電容式耦合電漿可在電漿增強CVD沉積室中進行。
電漿處理可在與沉積Si-C-N層相當的溫度完成,舉例來說,腔室的電漿處理區域可為約300℃或更低、腔室的電漿處理區域可為約250℃或更低、腔室的電漿處理區域可為約225℃或更低、腔室的電漿處理區域可為約200℃或更低等。舉例來說,電漿處理區域可具有約100℃至約300℃的溫度。基板的溫度可為約25℃或更高、基板的溫度可為約50℃或更高、基板的溫度可為約100℃或更高、基板的溫度可為約125℃或更高、基板的溫度可為約150℃或更高等。舉例來說,基板溫度可具有約25℃至約150℃的範圍。電漿處理區域中的壓力可取決於電漿處理(例如CCP對比ICP),但該壓力通常在mTorr至數十Torr的等級之範圍中。
經處理的Si-C-N層可選擇性曝露於一或多種蝕刻劑
(步驟110)。經處理的Si-C-N可具有比初始沉積的流動性Si-C-N層更低的濕蝕刻速度比(WERR)。可將WERR定義為Si-C-N層(例如Å/min)在特定蝕刻劑(例如稀釋的HF、熱磷酸)中的相對蝕刻速度,該相對蝕刻速度是與形成在相同基板上的熱生長氧化矽層之蝕刻速度相比。1.0的WERR是意謂討論中的層具有與熱氧化物層相同的蝕刻速度,而大於1的WERR是意謂該層之蝕刻速度比熱氧化物層之蝕刻速度快。電漿處理使沉積的Si-C-N層對蝕刻更有抗性,因而降低該Si-C-N層之WERR。
對於氧化矽與氮化矽兩者而言,經處理的Si-C-N層對於濕蝕刻劑可具有提高的蝕刻抗性(即較低的WERR水平)。舉例來說,Si-C-N層的電漿處理可降低對於稀釋的氫氟酸(DHF)之WERR水平,氫氟酸為現有用於氧化物的濕蝕刻劑,而且Si-C-N層的電漿處理也可降低對於熱磷酸之WERR水平,熱磷酸為現有用於氮化物的濕蝕刻劑。因此,經處理的Si-C-N層可對包括氧化物與氮化物兩種蝕刻步驟的蝕刻製程製作良好的阻擋及/或蝕刻終止層。
可實施本發明實施例的沉積室可包括高密度電漿化學氣相沉積(HDP-CVD)腔室、電漿增強化學氣相沉積(PECVD)腔室、次大氣壓化學氣相沉積(SACVD)腔室以
及熱化學氣相沉積腔室,還有其他類型的腔室。可實施本發明實施例的CVD系統之具體實例包括CENTURA ULTIMA® HDP-CVD腔室/系統及PRODUCER® PECVD腔室/系統,該等腔室/系統可向美國加州聖大克勞拉市的應用材料公司(Applied Materials,Inc.of Santa Clara,Calif.)購得。
可與本發明之示例性方法一起使用的基板處理腔室之實例可包括該等圖示且描述於共同受讓給Lubomirsky等人、於2006年5月30日提出申請及標題為「用於介電質縫隙填充之處理腔室(PROCESS CHAMBER FOR DIELECTRIC GAPFILL)」的美國臨時專利申請案第60/803,499號,為了所有的目的以引用方式將該美國臨時專利申請案之全部內容併入本文中。另外的示例性系統可包括該等圖示且描述於美國專利第6,387,207號與第6,830,624號中者,為了所有的目的以引用方式將該等美國專利之內容併入本文中。
可將沉積系統之實施例整合於較大的製造系統中,以生產積體電路晶片。第2圖圖示一個該種系統200,依據揭示的實施例之系統200由沉積腔室、烘烤腔室及硬化腔室所構成。於該圖中,一對FOUP(前開一致化箱)202供應基質基板(例如直徑300 mm的晶圓),機械手臂204接收該等基質基板,並在該等基質基板被放入晶圓處理室208a-f其中之一者之前將該等基質基板放入低壓承載區206。可以使用第二機械手臂210來將基板晶
圓從承載區206傳送至處理室208a-f並回傳。
處理室208a-f可包括一或多個用以沉積、退火、硬化及/或蝕刻基板晶圓上的流動性介電薄膜之系統部件。在一個架構中,可使用兩對處理室(例如208c-d與208e-f)來將流動性介電材料沉積在基板上,而且可使用第三對處理室(例如208a-b)來使沉積的介電質退火。在另一個架構中,可以架設相同的兩對處理室(例如208c-d與208e-f)皆來將流動性介電薄膜沉積在基板上並使基板上的流動性介電薄膜退火,同時可使用第三對腔室(例如208a-b)來進行沉積薄膜之紫外線(UV)或電子束(E-beam)硬化。在仍另一個架構中,可以架設全部三對腔室(例如208a-f)來沉積及硬化基板上的流動性介電薄膜。在又另一個架構中,可以使用兩對處理室(例如208c-d與208e-f)皆來沉積及紫外線或電子束硬化流動性介電質,同時可使用第三對處理室(例如208a-b)來進行介電薄膜的退火。可以在圖示於不同實施例中、與製造系統分離的腔室中進行任何一或多個描述的製程。
另外,可將一或多個處理室208a-f架設為濕處理室,該等處理室包括在包含濕氣的氛圍中加熱流動性介電薄膜。因此,系統200之實施例可包括濕處理室208a-b與退火處理室208c-d,以對沉積的介電薄膜進行濕與乾退火兩者。
第3A圖為依據所揭示實施例的基板處理室300。遠端
電漿系統(RPS)310可處理氣體,該氣體接著移動通過氣體入口配件311。在氣體入口配件311內可看到兩個不同的氣體供應通道,第一通道312攜載通過遠端電漿系統(RPS)310的氣體,而第二通道313繞過RPS310。在揭示的實施例中,可將第一通道312用於製程氣體並將第二通道313用於處理氣體。圖示在蓋體(或傳導頂部)321與穿孔的隔板353之間具有絕緣環324,絕緣環324容許相對於穿孔的隔板353將AC電位施加於蓋體321。製程氣體移動通過第一通道312而進入腔室電漿區320,並且製程氣體單獨被腔室電漿區320中的電漿激發,或是製程氣體被腔室電漿區320中的電漿與RPS 310的組合激發。在本文中可將腔室電漿區320及/或RPS 310的組合指稱為遠端電漿系統。穿孔的隔板(亦指稱為噴頭)353將腔室電漿區320與噴頭353下方的基板處理區370分隔。噴頭353容許電漿存在於腔室電漿區320中,以避免直接激發基板處理區370中的氣體,同時仍容許被激發的物種從腔室電漿區320移動進入基板處理區370。
噴頭353位於腔室電漿區320與基板處理區370之間,並且噴頭353容許在腔室電漿區320內產生的電漿流出物(前驅物或其他氣體之激發衍生物)通過複數個穿孔356,該複數個穿孔356貫穿板的厚度。噴頭353也具有一或多個中空容積351,中空容積351可被蒸汽或氣體形式的前驅物(如含矽前驅物)填充,而且中空
容積351可穿過小孔355而進入基板處理區370但不直接進入腔室電漿區320。在本揭示實施例中,噴頭353比穿孔356之最小直徑350的長度更厚。為了維持從腔室電漿區320滲出到基板處理區370的激發物種之顯著濃度,可藉由形成部分貫穿噴頭353的穿孔356之較大直徑部分來限縮穿孔之最小直徑350的長度326。在揭示的實施例中,穿孔356之最小直徑350的長度可與穿孔356之最小直徑屬於相同量級或屬於比穿孔356之最小直徑更小的量級。
在圖示的實施例中,噴頭353可分配(經由穿孔356)製程氣體,製程氣體含有氧、氫及/或氮及/或該種製程氣體在腔室電漿區320中被電漿激發之電漿流出物。在實施例中,經由第一通道312導入RPS 310及/或腔室電漿區320的製程氣體可含有氧(O2)、臭氧(O3)、N2O、NO、NO2、NH3、包括N2H4之NxHy、矽烷、二矽烷、TSA、DSA以及烷基胺中之一或多種。製程氣體也可包括載體氣體,如氦、氬、氮(N2)等。第二通道313也可傳送製程氣體及/或載體氣體,及/或用以從生長中的或初沉積的薄膜中移除不想要成分的薄膜硬化氣體(例如O3)。電漿流出物可包括製程氣體的離子化或中性衍生物,而且在本文中也可參照導入的製程氣體之原子組分將電漿流出物指稱為氧基前驅物及/或氮基前驅物。
在實施例中,穿孔356的數量可介於約60與約2000之間。穿孔356可具有各式各樣的形狀,但最簡單的是
將穿孔356做成圓形。在揭示的實施例中,穿孔356的最小直徑350可介於約0.5 mm與約20 mm之間,或穿孔356的最小直徑350可介於約1 mm與約6 mm之間。在選擇穿孔的剖面形狀上也有緯度之分,穿孔的剖面形狀可製成圓錐形、圓柱形或上述兩種形狀之組合。在不同的實施例中,用以將氣體導入基板處理區370的小孔355之數量可介於約100與約5000之間或該數量可介於約500與約2000之間。小孔355的直徑可介於約0.1 mm與約2 mm之間。
第3B圖為依據揭示的實施例用於處理室的噴頭353之底部視圖。噴頭353與第3A圖中圖示的噴頭對應,繪示的穿孔356在噴頭353底部具有較大的內徑(ID),而且繪示的穿孔356在噴頭353頂部具有較小的ID。小孔355大致上均勻地分佈於噴頭表面上,小孔355甚至分佈於穿孔356之間,以有助於提供比本文中所述的其他實施例更均勻的混合。
當抵達通過噴頭353中的穿孔356之電漿流出物與抵達通過小孔355(起源於中空容積351)之含矽前驅物結合時,在基板處理區370內由臺座(未圖示)支撐的基板上便產生示例性薄膜。雖然可以配備基板處理區370來供應用於其他製程(如硬化)的電漿,然而在生長示例性薄膜的過程中基板處理區370中無電漿存在。
可以在噴頭353上方的腔室電漿區320中或是在噴頭353下方的基板處理區370中激起電漿。電漿存在於腔
室電漿區320中,以由含氮氫的氣體流入物產生氮基前驅物。將通常在射頻(RF)範圍中的AC電壓施加於處理室的傳導頂部321與噴頭353之間,以於沉積過程中在腔室電漿區320中激起電漿。RF電源產生13.56 MHz的高RF頻率,但RF電源也可產生其他單獨的頻率或與13.56 MHz的頻率組合之頻率。示例性的RF頻率包括微波頻率,如2.4 GHz的微波頻率。在本發明的實施例中,在沉積流動性薄膜的過程中,頂部電漿功率可大於或約為1000瓦特、頂部電漿功率可大於或約為2000瓦特、頂部電漿功率可大於或約為3000瓦特或是頂部電漿功率可大於或約為4000瓦特。
當在第二硬化階段或清洗基板處理區370邊緣的內部表面期間開啟基板處理區370中的底部電漿時,可使頂部電漿處於低功率或無功率。藉由在噴頭353與臺座或腔室底部之間施加AC電壓,以激起基板處理區370中的電漿。當電漿存在時,可將清洗氣體導入基板處理區370。
臺座可具有熱交換通道,熱交換流體流經該熱交換通道,以控制基板的溫度。此種架構容許基板溫度被冷卻或加熱,以將基板維持於相對低溫(從室溫至約120℃)。熱交換流體可包含乙二醇與水。也可使用內嵌式單迴圈內嵌加熱元件(設以造成二個平形同心圓形式的完整迴圈)來電阻式加熱臺座之晶圓支撐淺盤(較佳為鋁、陶瓷或上述物質之組合),以達成相對高溫(從約120℃至
約1100℃)。加熱元件的外圈部分可在鄰接支撐淺盤周圍之處運作,而加熱元件的內圈部分在具有較小外徑的同心圓路徑上運作。到加熱元件的配線通過臺座的桿座。
基板處理系統受系統控制器控制,在示例性實施例中,系統控制器包括硬式磁碟機、軟式磁碟機以及處理器。該處理器含有單板電腦(SBC)、類比與數位輸入/輸出板、介面板以及步進馬達控制板。CVD系統的各種部件符合Versa模件歐洲的(Versa Modular European,VME)標準,VME標準定義寬的卡片機架及連接器尺寸與類型。VME標準亦定義匯流排結構為具有16位元資料匯流排與24位元定址匯流排。
系統控制器控制沉積系統的所有活動,系統控制器執行系統控制軟體,系統控制軟體為儲存於電腦可讀媒體之電腦程式。較佳的,該媒體為硬式磁碟機,但是該媒體也可以是其他種類的記憶體。電腦程式包括指令集,該等指令集指定時間、氣體混合物、腔室壓力、腔室溫度、RF功率等級、基座位置,以及其他特殊製程的參數。也可使用儲存在其他記憶體裝置(例如包括軟碟或其他合適的磁碟機)的電腦程式來指示系統控制器。
可以使用由系統控制器執行的電腦程式產品來實施在基板上沉積薄膜堆疊(例如依序沉積含矽氮氫層以及之後的含矽氧碳層)、將薄膜轉化為氧化矽之製程或是清洗腔室之製程。可以任何現有的電腦可讀程式語言來撰寫電腦程式編碼:例如68000組合語言、C、C++、Pascal、
Fortran或其他電腦可讀程式語言。使用現有的文字編輯器將適當的程式編碼輸入單一檔案或多個檔案中,並且將該適當的程式編碼儲存或體現於電腦可用媒體中,如電腦的記憶體系統。假使輸入的編碼文字為高階語言,則編譯編碼,之後並將產生的編譯編碼與預編譯的微軟視窗®(Microsoft Windows®)程式館常式之目標編碼聯結。為執行該經聯結、編譯的目標編碼,系統使用者喚起目標編碼、致使電腦系統載入記憶體中的編碼,然後CPU讀取並執行編碼以進行程式中確認的任務。
使用者與控制器之間的介面係經由平板觸摸敏感式監視器。在較佳的實施例中使用二個監視器,一個監視器組裝於潔淨室牆壁中供操作員使用,而另一個監視器組裝於牆壁外面供服務技師使用。該二個監視器可同時顯示相同的資訊,在任一案例中,於同一時間只有一個監視器接受輸入。為了要選擇特殊的畫面或功能,操作員可觸碰觸摸敏感式監視器的指定區域。經觸碰的區域會改變該區域彰顯的顏色,或者會顯示出新的選單或畫面,以確認操作員與觸摸敏感式監視器之間的溝通。可以使用其他的裝置(如鍵盤、滑鼠或其他的指示或溝通裝置)來取代該觸摸敏感式監視器,或是除了該觸摸敏感式監視器之外可同時使用該等其他的裝置,以容許使用者與系統控制器溝通。
本文中使用的「基板」可為支撐基板,該支撐基板上可有或無層形成。該支撐基板可為絕緣體或具有各種摻
雜濃度與濃度曲線的半導體,而且例如該支撐基板可以是半導體基板,該半導體基板的類型與製造積體電路所使用的類型相同。用語「前驅物」係用以指稱任何參與反應以從表面移除材料或是沉積材料於表面上的製程氣體。在「激發狀態」中的氣體係描述其中至少某些氣體分子處於振動激發狀態、解離狀態及/或離子化狀態的氣體。氣體(或前驅物)可以是二或更多種氣體(或前驅物)的組合。「自由基前驅物」係用以描述電漿流出物(處於激發狀態的氣體,該氣體退去電漿),該電漿流出物參與反應以從表面移除材料或是沉積材料於表面上。「氮自由基前驅物」為含有氮的自由基前驅物,而「氫自由基前驅物」為含有氫的自由基前驅物。片語「惰性氣體」係指稱當蝕刻或被整合進入薄膜中時任何不形成化學鍵結的氣體。示例性的惰性氣體包括鈍氣,但也可包括其他的氣體,只要當(通常是)微量的該氣體被捕捉於薄膜中時沒有化學鍵結形成即可。
貫穿全文使用用語「縫隙」,但並無暗示蝕刻的幾何形狀具有大的水平深寬比之意。從表面的上方看,溝槽可能會呈現圓形、卵形、多邊形、矩形或各種其他的形狀。本文中使用的保形層係指稱表面上大致上均勻的材料層具有與該表面相同的形狀,即該層的表面與將被覆蓋的表面大致上是平行的。在本技術領域中具有通常知識之人士將理解到,所沉積的材料可能無法100%保形,因此用語「大致上」容許可接受的公差。
第4圖圖示沉積的Si-C-N在以誘導式耦合電漿處理之前與之後的FTIR光譜,初始沉積的流動性Si-C-N層係由1,3,5-三矽戊烷與氨氣體混合物的電漿流出物之化學氣相沉積所沉積,該氨氣體混合物係於沉積室外部的遠端電漿單元中高能化。
第4圖中的圖圖示初沉積的流動性Si-C-N層在約2250 cm-1具有強的Si-H尖峰。在HDP電漿處理之後,該尖峰幾乎已經完全消失,表示初始流動性層中大部分的(若非全部)Si-H鍵結已被該電漿處理移除。
有了描述的幾個實施例,在本技術領域中具有通常知識者將理解,可以在不偏離本發明的精神下使用各種修飾、替代結構以及等同物。此外,並未描述數個習知的製程與元件,以避免不必要地混淆本發明。因此,不應將以上描述視為對於本發明範圍之限制。
當提供數值的範圍時,應瞭解到,除非內文以其他方式清楚指明,否則在該範圍的上限與下限之間、每個到下限單位的十分之一之中間值亦為具體揭示的。在陳述範圍中的任何陳述值或中間值與該陳述範圍中的任何其他陳述值或中間值之間的每個較小範圍亦被涵括。該等較小範圍的上限與下限可獨立地被包括或排除於該範圍中,而且不論是該等較小範圍包括任一限值、不包括二限值或是包括二限值,該等較小範圍中的每個範圍亦被涵括於本發明中,取決於該陳述範圍中任何經具體排除
的限值。當該陳述範圍包括該等限值中之一者或二者時,排除該等包括的限值中之任一者或二者的範圍亦被包括。
除非內文以其他方式清楚指明,否則本文中與隨附申請專利範圍中使用的單數形「一」及「該」包括複數的指示對象。因此,舉例來說,提及「一製程」係包括複數個該種製程,而提及「該前驅物」係包括提及一或多個前驅物及該一或多個前驅物之等同物(為本技術領域中具有通常知識者所習知者),以此類推。
同樣地,當用於本說明書中及以下申請專利範圍中時,字眼「包含」與「包括」意欲指明陳述的特徵、整數、成分或步驟之存在,但該等字眼並不排除一或多個其他的特徵、整數、成分、步驟、動作或基團的存在或加入。
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200‧‧‧系統
202‧‧‧FOUP
204‧‧‧機械手臂
206‧‧‧承載區
208a‧‧‧處理室
208b‧‧‧處理室
208c‧‧‧處理室
208d‧‧‧處理室
208e‧‧‧處理室
208f‧‧‧處理室
210‧‧‧第二機械手臂
300‧‧‧基板處理室
310‧‧‧遠端電漿系統
311‧‧‧氣體入口配件
312‧‧‧第一通道
313‧‧‧第二通道
320‧‧‧腔室電漿區
321‧‧‧蓋體
324‧‧‧絕緣環
326‧‧‧長度
350‧‧‧最小直徑
351‧‧‧中空容積
353‧‧‧穿孔的隔板/噴頭
355‧‧‧小孔
356‧‧‧穿孔
370‧‧‧基板處理區
藉由參照本說明的剩餘部分及圖式可以對本發明的本質與優點有進一步的瞭解,其中在該幾張圖式中從頭至尾使用類似的元件符號來指稱類似的元件。在某些實例中,下標係與元件符號有關,並且下標接續在連字號後面以表示多個類似元件中之一者。當提及元件符號而未敘明存在的下標時,則意欲指稱該多個類似元件之全部。
第1圖係圖示於基板上形成含矽碳氮的介電層之方法
中的精選步驟之流程圖;第2圖圖示依據本發明的實施例之基板處理系統;第3A圖圖示依據本發明的實施例之基板處理室;第3B圖圖示依據本發明的實施例之氣體分配噴頭;以及第4圖圖示進行電漿處理之前與之後的矽碳氮薄膜之紅外線光譜。
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Claims (20)
- 一種於一半導體基板上形成一介電層之方法,該方法包含以下步驟:提供一含矽前驅物及一高能化含氮前驅物至一化學氣相沉積室;使該含矽前驅物與該高能化含氮前驅物於該化學氣相沉積室中反應,而於該基板上沉積一流動性矽碳氮材料;以及處理該流動性矽碳氮材料以於該半導體基板上形成該介電層。
- 如請求項1所述之方法,其中該含矽前驅物包含1,3,5-三矽戊烷(1,3,5-trisilapentane)、1,4,7-三矽庚烷(1,4,7-trisilaheptane)、二矽環丁烷(disilacyclobutane)、三矽環己烷(trisilacyclohexane)、3-甲基矽烷、矽環戊烯(silacyclopentene)、矽環丁烷(silacyclobutane)或三甲基矽基乙炔(trimethylsilylacetylene)。
- 如請求項1所述之方法,其中該含矽前驅物包含:(i)SiR4、Si2R6、Si3R8、Si4R10或Si5R12,其中每一R基團係獨立為氫(-H)或一飽和或不飽和烷基基團;(ii)一具有式R3Si-[CH2]n-SiR3的矽基烷或矽基烯, 其中n為1至10之一整數,及每一R基團係獨立為一氫(-H),或一飽和或不飽和烷基基團;(iii)一具有式R3Si-[CR2]x-SiR2-[CR2]y-SiR3的矽基烷或矽基烯,其中x與y係獨立為1至10之一整數,及每一R基團係獨立為一氫(-H),或一飽和或不飽和烷基基團;(iv)一選自由下列所組成的群組之矽環烷或矽環烯:矽環丙烷(silacyclopropanes)、矽環丁烷(silacyclobutanes)、矽環戊烷(silacyclopentanes)、矽環己烷(silacyclohexanes)、矽環庚烷(silacycloheptanes)、矽環辛烷(silacyclooctanes)、矽環壬烷(silacyclononanes)、矽環丙烯(silacyclopropenes)、矽環丁烯(silacyclobutenes)、矽環戊烯(silacyclopentenes)、矽環己烯(silacyclohexenes)、矽環庚烯(silacycloheptenes)、矽環辛烯(silacyclooctenes)及矽環壬烯(silacyclononenes);(v)H4-x-yCXy(SiR3)x,其中x為1、2、3或4,y為0、1、2或3,每一X係獨立為一氫或鹵素(例如F、Cl、Br),而且每一R係獨立為一氫(-H)或一烷基基團;(vi)(SiR3)xC=C(SiR3)x,其中x為1或2,而且每一R係獨立為一氫(-H)或一烷基基團;或(vii)R-[(CR' 2)x-(SiR" 2)y-(CR' 2)z]n-R,其中每一R、R'及R"係獨立為一氫、一烷基基團、一不飽和烷基基 團、一矽烷基團或-[(CH2)x1-(SiH2)y1-(CH2)z1]n1-R''',其中x1、y1及z1係獨立為0至10之一數,及n1為0至10之一數;以及其中x、y及z係獨立為0至10之一數,及n為0至10之一數。
- 如請求項1所述之方法,其中該含矽前驅物包含一含矽氮前驅物,該含矽氮前驅物係選自由以下所組成的群組:(i)R4-xSi(NR2)x,其中x可為1、2、3或4,及每一R係獨立為一氫(-H)或一烷基基團;(ii)R4-yN(SiR3)y,其中y可為1、2或3,及每一R係獨立為一氫(-H)或一烷基基團;或(iii)一經取代或未經取代的環結構,該環結構於環中包含至少一個Si原子及至少一個氮原子。
- 如請求項1所述之方法,其中該含矽前驅物包含1,3,5-三矽戊烷或1,4,7-三矽庚烷中之一者。
- 如請求項1所述之方法,其中該高能化含氮前驅物包含高能化氨或氨之一高能化碎體。
- 如請求項1所述之方法,其中該高能化氨係於一遠端 電漿系統中產生,該遠端電漿系統與該化學氣相沉積室流體耦接。
- 如請求項1所述之方法,其中該流動性矽碳氮材料包含Si-H鍵結。
- 如請求項8所述之方法,其中處理該流動性矽碳氮材料之該步驟減少該材料中之Si-H鍵結數量。
- 如請求項1所述之方法,其中處理該流動性矽碳氮材料之該步驟包含:使該材料曝露於一電漿。
- 如請求項10所述之方法,其中用於處理該流動性矽碳氮材料之該電漿係位於該化學氣相沉積室中。
- 如請求項10所述之方法,其中該電漿為一誘導式耦合電漿或一電容式耦合電漿。
- 一種處理一流動性矽碳氮層以降低該層之一濕蝕刻速度比(WERR)的方法,該方法包含以下步驟:藉由一含矽前驅物及一活化氮前驅物之化學氣相沉積而在一基板上形成該流動性矽碳氮層;使該流動性矽碳氮層曝露於電漿,其中該電漿曝露減少該層中之Si-H鍵結數量並增加該層中之Si-C鍵結 數量,以及其中該電漿曝露降低該層之WERR。
- 如請求項13所述之方法,其中該流動性含矽前驅物包含1,3,5-三矽戊烷(1,3,5-trisilapentane)、1,4,7-三矽庚烷(1,4,7-trisilaheptane)、二矽環丁烷(disilacyclobutane)、三矽環己烷(trisilacyclohexane)、3-甲基矽烷、矽環戊烯(silacyclopentene)、矽環丁烷(silacyclobutane)或三甲基矽基乙炔(trimethylsilylacetylene)。
- 如請求項13所述之方法,其中該流動性含矽前驅物包含:(i)SiR4、Si2R6、Si3R8、Si4R10或Si5R12,其中每一R基團係獨立為氫(-H)或一飽和或不飽和烷基基團;(ii)一具有式R3Si-[CH2]n-SiR3的矽基烷或矽基烯,其中n為1至10之一整數,及每一R基團係獨立為一氫(-H),或一飽和或不飽和烷基基團;(iii)一具有式R3Si-[CR2]x-SiR2-[CR2]y-SiR3的矽基烷或矽基烯,其中x與y係獨立為1至10之一整數,及每一R基團係獨立為一氫(-H),或一飽和或不飽和烷基基團;(iv)一選自由下列所組成的群組之矽環烷或矽環烯:矽環丙烷(silacyclopropanes)、矽環丁烷(silacyclobutanes)、矽環戊烷(silacyclopentanes)、矽 環己烷(silacyclohexanes)、矽環庚烷(silacycloheptanes)、矽環辛烷(silacyclooctanes)、矽環壬烷(silacyclononanes)、矽環丙烯(silacyclopropenes)、矽環丁烯(silacyclobutenes)、矽環戊烯(silacyclopentenes)、矽環己烯(silacyclohexenes)、矽環庚烯(silacycloheptenes)、矽環辛烯(silacyclooctenes)及矽環壬烯(silacyclononenes);(v)H4-x-yCXy(SiR3)x,其中x為1、2、3或4,y為0、1、2或3,每一X係獨立為一氫或鹵素(例如F、Cl、Br),而且每一R係獨立為一氫(-H)或一烷基基團;(vi)(SiR3)xC=C(SiR3)x,其中x為1或2,而且每一R係獨立為一氫(-H)或一烷基基團;或(vii)R-[(CR' 2)x-(SiR" 2)y-(CR' 2)z]n-R,其中每一R、R'及R"係獨立為一氫、一烷基基團、一不飽和烷基基團、一矽烷基團或-[(CH2)x1-(SiH2)y1-(CH2)z1]n1-R''',其中x1、y1及z1係獨立為0至10之一數,及n1為0至10之一數,以及其中x、y及z係獨立為0至10之一數,及n為0至10之一數。
- 如請求項13所述之方法,其中該流動性含矽前驅物包含一含矽氮前驅物,該含矽氮前驅物係選自由以下所 組成的群組:(i)R4-xSi(NR2)x,其中x可為1、2、3或4,及每一R係獨立為一氫(-H)或一烷基基團;(ii)R4-yN(SiR3)y,其中y可為1、2或3,及每一R係獨立為一氫(-H)或一烷基基團;或(iii)一經取代或未經取代的環結構,該環結構於環中包含至少一個Si原子及至少一個氮原子。
- 如請求項13所述之方法,其中該活化氮前驅物包含氨或一氨碎體,該氨碎體已曝露於一電漿。
- 如請求項13所述之方法,其中該電漿曝露減少該矽碳氮層中之C-H鍵結數量並增加該矽碳氮層中之Si-Si鍵結數量、Si-N鍵結數量及C-N鍵結數量。
- 如請求項13所述之方法,其中該電漿為一誘導式耦合電漿或一電容式耦合電漿。
- 如請求項13所述之方法,其中該電漿曝露減少該矽碳氮層於稀釋氫氟酸與熱磷酸兩者中之WERR。
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- 2012-08-21 US US13/590,611 patent/US20130217240A1/en not_active Abandoned
- 2012-09-06 WO PCT/US2012/053999 patent/WO2013036667A2/en active Application Filing
- 2012-09-06 KR KR1020147009305A patent/KR20140066220A/ko not_active Application Discontinuation
- 2012-09-07 TW TW101132769A patent/TW201316407A/zh unknown
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TWI636011B (zh) * | 2013-08-16 | 2018-09-21 | 美商恩特葛瑞斯股份有限公司 | 基板內矽佈植及其之矽前驅物組合物之供給 |
TWI654136B (zh) | 2013-08-16 | 2019-03-21 | 美商恩特葛瑞斯股份有限公司 | 基板內矽佈植及其之矽前驅物組合物之供給 |
TWI742327B (zh) * | 2017-12-20 | 2021-10-11 | 日商國際電氣股份有限公司 | 半導體裝置之製造方法、基板處理方法、基板處理裝置及程式 |
US11746416B2 (en) | 2017-12-20 | 2023-09-05 | Kokusai Electric Corporation | Method of processing substrate and manufacturing semiconductor device by forming film containing silicon |
Also Published As
Publication number | Publication date |
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WO2013036667A3 (en) | 2013-05-02 |
US20130217240A1 (en) | 2013-08-22 |
WO2013036667A2 (en) | 2013-03-14 |
KR20140066220A (ko) | 2014-05-30 |
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