TWI386414B - 包含碳氮化矽及氧碳氮化矽薄膜之含矽薄膜之低溫化學氣相沉積用組成物及方法 - Google Patents
包含碳氮化矽及氧碳氮化矽薄膜之含矽薄膜之低溫化學氣相沉積用組成物及方法 Download PDFInfo
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- 238000005229 chemical vapour deposition Methods 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 title description 13
- 229910052710 silicon Inorganic materials 0.000 title description 4
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- 239000010703 silicon Substances 0.000 title 3
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- 125000003118 aryl group Chemical group 0.000 claims description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 15
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
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- 125000004663 dialkyl amino group Chemical group 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical group CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 2
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- YMEKHGLPEFBQCR-UHFFFAOYSA-N 2,2,3,3,5,5-hexachloro-1,4-dioxane Chemical compound ClC1(OC(C(OC1)(Cl)Cl)(Cl)Cl)Cl YMEKHGLPEFBQCR-UHFFFAOYSA-N 0.000 description 1
- QDKSGHXRHXVMPF-UHFFFAOYSA-N 2,2-dimethylundecane Chemical compound CCCCCCCCCC(C)(C)C QDKSGHXRHXVMPF-UHFFFAOYSA-N 0.000 description 1
- 239000012695 Ce precursor Substances 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 125000005270 trialkylamine group Chemical group 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
本發明係大致關於新穎的含矽前驅物及於半導體裝置之製造中使用該前驅物形成含矽薄膜。更明確言之,本發明係關於含矽前驅物及使用低溫(T<550℃)化學氣相沉積(CVD)方法於基板上形成含矽薄膜(例如,包含碳氮化矽及氧碳氮化矽之薄膜)的方法。
在半導體製造中,化學惰性介電材料(諸如,氮化矽(Si3N4)、氧氮化矽(SiOxNy)及/或二氧化矽(SiO2))之薄(例如,厚度<1,000奈米)被動層被廣泛使用於微電子裝置結構中,以作為多層結構之結構元件,諸如側壁隔離片元件、擴散罩、氧化障壁、溝渠隔離塗層、金屬間介電材料、鈍化層及蝕刻停止層。
近年來的研究顯示將碳加入(10-15%)於氮化矽薄膜中有利於電晶體側壁隔離片應用的薄膜品質。碳與氮化矽或氧化矽之混合物亦有利於位在低介電常數(低k)層之間的蝕刻停止層及覆蓋層。此外,氮化矽之前金屬介電質(PMD)襯裡需要蝕刻選擇性及擴散障壁性質,其可經由將碳加入至氮化矽中而增進。
顯現氮化矽及碳化矽性質之碳氮化矽(Si-C-N)既耐溫亦抗氧化。因此,Si-C-N材料被研究使用作為供Cu雙重鑲嵌(dual damascene)製程用之硬遮罩、蝕刻停止層或鈍化層。
Si-C-N層一般係使用各種電漿增進化學沉積技術(PECVD)成長。
利用CVD技術沉積含矽薄膜係用於形成此等Si-C-N薄膜之一項極引人矚目的方法。為此,一般使用單矽烷、烴類、及氨或氮之混合物於在高溫(T~1300 K)下使用CVD合成Si-C-N薄膜。舉例來說,已利用微波電漿增進CVD(PECVD)使用H2、CH4、N2及SiH4氣體之混合物在高於800℃之溫度下成長Si-C-N之結晶薄膜。然而,此等混合物有爆炸性及可燃性的傾向。(參見,Chen,L.C.等人,Applied Physics Letters,72,2463-2465(1998))。新近已使用PECVD在350℃至400℃下使用三甲基矽烷(3MS)、氦及氨之混合物沉積Si-C-N薄膜(參見,遠見(Foresight),2003年4月,台灣應用材料(Applied Materials Taiwan)之刊物)。此揭示之沉積需要高電漿密度,若將其使用於「前端(front end)」(例如,PMD-襯裡)時,其會損壞裝置結構。
為可與下一代的IC裝置製造相容,側壁隔離片需利用熱CVD製程在低沉積溫度(例如,低於約550℃之溫度,以約530℃較佳)下沉積。由於嚴苛的仿形度需求及鄰近於電晶體通道,因而不允許使用電漿。目前使用的前驅物,諸如BTBAS,需要相當高的前驅物流率,且於此等溫度下具有極低的沉積速率,而導致非常高的加工成本。因此,對於供此等熱沉積製程用之適當前驅物組成物有顯著的需求。其中特別重要者為包含適當比例之矽、氮及碳的揮發性有機矽前驅物。
此外,為可與下一代的IC裝置製造相容,PMD襯裡需在低於約450℃(以約400℃較佳)之溫度下沉積。對此應用,低能量密度電漿將可接受。此外,待與低k介電質及銅佈線整合之蝕刻停止層及覆蓋層需在低於約400℃(以低於約350℃較佳)之溫度下沉積。此等層需具有高結構完整性、對於銅擴散的良好障壁性質、及顯著低於氮化矽的介電常數。對於蝕刻停止層及覆蓋層應用,PECVD亦可接受。同樣地,包含適當比例之矽、氮及碳的揮發性有機矽前驅物為較佳。
先前吾人證實二矽烷前驅物可在低溫下提供高沉積速率。舉例來說,氮化矽薄膜可利用CVD在450℃下使用六乙醯胺基二矽烷(HEADS)前驅物及氨之混合物在26埃/分鐘之速率下沉積。不以理論為基礎,高成長速率係可歸因於在二矽烷化合物中之弱的矽-矽鍵(其具有222仟焦耳/莫耳之鍵能)。此外,由於反應物隨溫度之增高而自表面脫附,因而據報告較高溫於基板引起較低的沉積速率。值得注意地,具有弱Si-Si鍵之二矽烷(Si2H6)及六氯二矽烷(HCDS)(Si2Cl6)亦被視為具有潛力的前驅物,然而,其未提供碳原子來源。此外,氯會被加入至製得之晶片中,而會使晶片長期性能顯著地降低。
因此,技藝中持續需要用於形成含矽薄膜,諸如包括氧氮化矽、氮化矽、碳氮化矽及氧碳氮化矽之低k含矽薄膜的改良有機矽前驅物。
本發明係大致關於在半導體裝置之製造中形成含矽薄膜,及更明確言之,係關於新穎的矽前驅物及使用低溫(T<550℃)CVD方法於基板上形成含矽薄膜(諸如,含矽低k薄膜及包含碳氮化矽(Si-C-N)及氧碳氮化矽(Si-O-C-N)之薄膜)的方法。
本發明之一態樣係關於一種選自下列所構成之群組之矽化合物:(A)式:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x
之化合物,其中:R1、R2、及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基、芳烷基所構成之群組;及x係1或2;(B)式:
之化合物,其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基及芳烷基所構成之群組;及X、Y、及Z可彼此相同或不同,且各係獨立地選自H、
烷基、烷胺基、二烷胺基及烷醯肼基(alkylhydrazido)所構成之群組;其限制條件為當R1、R2、X及Y為甲基且R3為氫時,Z不可為氫;及(C)式:
之化合物,其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基及芳烷基所構成之群組;及X1、X2、Y1、Y2、Z1及Z2可彼此相同或不同,且各係獨立地選自H、烷基、烷胺基、二烷胺基及烷醯肼基所構成之群組,其限制條件為當各個R3為H且各個R1、X1、X2、Y1與Y2為甲基時,那時兩個R2不為H或甲基。
本發明之另一態樣係關於一種於基板上形成含矽薄膜之方法,其包括使基板於化學氣相沉積條件於低於600℃之溫度下與選自下列所構成之群組之矽化合物之蒸氣接觸:(A)式:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x
之化合物,其中:
R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基、芳烷基所構成之群組;及x係1或2;(B)式:
之化合物,其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基及芳烷基所構成之群組;及X、Y、及Z可彼此相同或不同,且各係獨立地選自H、烷基、烷胺基、二烷胺基及烷醯肼基所構成之群組;其限制條件為當R1、R2、X及Y為甲基且R3為氫時,Z不可為氫;(C)式:
之化合物,其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基及芳烷基所構成之群組;及
X1、X2、Y1、Y2、Z1及Z2可彼此相同或不同,且各係獨立地選自H、烷基、烷胺基、二烷胺基及烷醯肼基所構成之群組;及(D)式:(i)(R 1 R 2 N) 2 Si:,(ii)(R 1 R 2 N) 2 Si=Si(NR 1 R 2 ) 2 ,及(iii)(R 1 R 2 N) 2 HSi-SiR 3 n H 3-n ,之化合物,其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C4烷基、胺基、矽基(-SiH3)及矽基之烴基衍生物(例如,-SiR3)所構成之群組;及0≦n≦3。
本發明之又另一態樣係關於一種製造式:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x
之矽化合物的方法,其中:R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基、芳烷基所構成之群組;及x係1或2;該方法包括使式XR1R2Si-SiXR1R2之二矽烷化合物與二級胺內(R2R3NH)及三級胺類(R1R2R3N)化合物反應,其中X係選自溴、氟及氯所構成之群組,而R1、R2及R3係如前所述,其之反應係根據下式:XR1R2Si-SiXR1R2+R2R3NH+R1R2R3N →
(R2R3N)3-xR1 xSi-SiR1 x(NR2R3)3-x
本發明之其他態樣、特徵及具體例將可由隨後之揭示內容及隨附之申請專利範圍而更加明白。
本發明係關於供於基板上在低溫下以CVD形成碳氮化矽及/或氧碳氮化矽薄膜用之新穎的矽前驅物,及關於利用此種前驅物形成此種薄膜之相關方法。
在一態樣中,本發明提供一種式:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x (1)
之化合物,其中:R1、R2、及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基、芳烷基所構成之群組;及x係1或2。
式(1)之化合物有用於利用化學氣相沉積,利用包括低於600℃之沉積溫度(低於550℃更佳)、及相關之壓力、濃度、流率及CVD技術的方法條件形成含矽薄膜,該等方法條件可基於本文之揭示內容而在一定應用之技藝技能內容易地決定。
文中定義之「含矽薄膜」係指氮化矽、氧氮化矽、碳氮化矽、氧碳氮化矽、低k含矽薄膜、高k閘矽酸鹽薄膜及低溫矽磊晶薄膜。
式(1)之較佳的化合物包括
Me2(NEt2)Si-Si(NEt2)Me2、Me2(NEtMe)Si-Si(NEtMe)Me2、及Me2(NMe2)Si-Si(NMe2)Me2。
式(1)之化合物係藉由式R1 2XSi-SiXR1 2之二矽烷化合物與二級胺類(R2R3NH)及三級胺類(R1R2R3N)化合物之反應而容易地合成得,其中X係選自溴、氟及氯所構成之群組,及R1、R2及R3係如前所述。舉例來說,Me2(NEt2)Si-Si(NEt2)Me2可根據以下反應製備得:Me4Si2Cl2+2 NEt3+2 HNEt2 → Me4Si2(NEt2)2+2 NEt3˙HCl
其如更完整說明於後文的實施例中。
本發明之另一態樣係關於一群經至少一烷基肼官能基取代之不含鹵素之矽烷或二矽烷衍生物,其可使用作為用於沉積含矽薄膜之CVD前驅物。
本發明之矽烷衍生物可以以下通式表示:
其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基及芳烷基所構成之群組;及X、Y、及Z可彼此相同或不同,且各係獨立地選自H、烷基、烷胺基、二烷胺基及烷醯肼基(例如,R1R2NNH-,其中R1及R2係與前文所述者相同)所構成之群組;其限制條件為當R1、R2、X及Y為甲基且R3為氫時,
Z不可為氫。
本發明之矽烷衍生物亦可以以下通式表示:
其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C5烷基、C3-C6環烷基、芳基及芳烷基所構成之群組;及X1、X2、Y1、Y2、Z1及Z2可彼此相同或不同,且各係獨立地選自H、烷基、烷胺基、二烷胺基及烷醯肼基所構成之群組,其限制條件為當各個R3為H且各個R1、X1、X2、Y1與Y2為甲基時,那時兩個R2不為H或甲基。
本發明之二矽烷衍生物化合物的特徵在於相對於Si-Si鍵對稱分佈的官能基較佳。
式(2)及(3)之化合物係藉由式R1 2XSi-SiXR1 2之二矽烷化合物與胺(R1R2R2N)化合物及肼化合物(H2NNR1 2)之反應而容易地合成得,其中X係選自溴、氟及氯所構成之群組,及R1、R2及R3係如前所述。舉例來說,Me2(Me2NNH)Si-Si(NHNMe2)Me2可根據以下反應製備得:Me4Si2Cl2+2 NEt3+2 H2NNMe2 → Me4Si2(NHNMe2)2+2 NEt3˙HCl
其如更完整說明於後文的實施例中。
式(2)及(3)之化合物有用於利用化學氣相沉積,利用
包括低於600℃之沉積溫度(低於550℃更佳)、及相關之壓力、濃度、流率及CVD技術的方法條件形成含矽薄膜,該等方法條件可基於本文之揭示內容而在一定應用之技藝技能內容易地決定。
可於低溫下(諸如在自約350℃至約550℃之範圍內)進行CVD製程,以於半導體製造中前及後金屬沉積氮化矽或氧氮化矽之薄(例如,500埃至1微米厚度)介電薄膜,或以其他方式於不同基板上形成氮化矽或氧氮化矽陶瓷薄膜之另一類根據本發明之含矽前驅物包括式(4)之二胺基亞矽基及其之以式(5)及(6)表示之衍生物:(R 1 R 2 N) 2 Si: (4)
(R 1 R 2 N) 2 Si=Si(NR 1 R 2 ) 2 (5)
(R 1 R 2 N) 2 HSi-SiR 3 n H 3-n (6)
其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、C1-C4烷基、胺基、矽基(-SiH3)及矽基之烴基衍生物(例如,-SiR3)所構成之群組;及0≦n≦3。
以式(4)表示之二胺基亞矽基係二基根物種,其部分不穩定且易形成以式(5)及(6)表示之衍生物,而其他則相當穩定,且可容易地以其之二基根形式提供。
一範例的穩定亞矽基化合物包括以下的二胺基亞矽基:
此二胺基亞矽基於在甲苯中於150℃下沸騰4個月後仍維持不變。於220℃下發生熱分解。據認為此二胺基亞矽基之穩定性部分係由芳族穩定化作用所產生(參見,Denk,M.等人,J.Am.Chem.Soc.,116,2691-2692(1994))。
以式(4)表示之二胺基亞矽基可根據以下機構合成得(參見,West,R.、Denk,M.,Pure Appl.Chem.,68,785-788(1996)):
式(5)及(6)之化合物可根據以下所示之反應流程製造:
根據本文之教示,可藉由選擇式(1)-(6)之特定的含矽前驅物而調整利用相關CVD製程製得之介電薄膜的類型。舉例來說,可使用氨、氧或一氧化氮作為另一類的單一反應物於形成各別的氮化矽、氧氮化矽、碳氮化矽及/或氧碳氮化矽單成分薄膜,或可利用式(1)-(6)前驅物之選定的一者,將二或多種此等反應物之混合物使用於CVD製程中,以形成相對的多成分薄膜、或分級組成物薄膜。或者,可將式R1R2R3N之單、二及三烷基胺使用作為反應物,其中R1、R2及R3可彼此相同或不同,且各係獨立地選自H、及C1-C4烷基所構成之群組。此外,前驅物氣體中可存在惰性遞送氣體,其包括氦、氬及氮。
在應用時,使含矽前驅物與期望的共反應物以任何適當的方式反應,例如,於單一晶圓CVD室中,或於包含多個晶圓之爐中,利用包括低於600℃之沉積溫度(低於<550℃更佳)、及相關之壓力、濃度、流率及CVD技術的方法條件,其可基於本文之揭示內容而在一定應用之技藝技能
內容易地決定。舉例來說,當沉積側壁間隔片、PMD襯裡、或蝕刻止停及覆蓋層時,應分別使用低於550℃、低於450℃、及低於400℃之溫度。關於壓力,沉積壓力可在自約1托爾(Torr)至約80托爾之範圍內。
本發明之特徵及優點由以下之說明性及非限制性實施例作更完整展示。
實施例1 Me2(NEt2)Si-Si(NEt2)Me2之合成
將300毫升之己烷及350毫升(1.6 M,560毫莫耳)之正丁基鋰的己烷溶液混合於1公升之燒瓶中。在0℃下於此溶液中添加41克之HNEt2(560毫莫耳)。立即觀察到白色沉澱物質。當添加完成時,使反應燒瓶升溫至室溫,並再多攪拌一小時。接著在室溫下將溶於100毫升乙醚中之50克Me4Si2Cl2(270毫莫耳)緩慢加至燒瓶。將混合物攪拌隔夜,並於室溫下過濾。於自濾液移除揮發物後,得到粗製產物(59克(227毫莫耳),85%產率)。經由真空蒸餾得到純產物(於190毫托爾下之沸點~62℃)。1H NMR(C6D6):0.26(s,12 H,-CH 3 Si);1.00(t,12 H,-CH 3 CH2N);2.83(q,8H,-CH3CH 2 N)。13C{1H}NMR(C6D6):δ0.33(-CH 3 Si);16.2(-NCH2CH 3 );41.3(-NCH 2 CH3)。質譜:m/z 260[M+];188[M+ -(-NEt2)];130[M+ -(-SiMe2(NEt2))]。C12H32N2Si2:實測(理論),C:54.98%(55.31%),H:12.41%(12.38%),N:10.66%(10.75%)。
圖1顯示STA數據,其指示Me2(NEt2)Si-Si(NEt2)Me2之T50值係約160℃,證實對於化學氣相沉積的良好揮發
性及輸送性質。
實施例2 Me2(Me2NNH)Si-Si(NHNMe2)Me2之合成
將3公升燒瓶裝填包含2.5公升己烷、50克(267毫莫耳)Me4Si2Cl2、及57克(561毫莫耳)無水NEt3之溶液。在室溫下將溶解於100毫升乙醚中之34克H2NNMe2(561毫莫耳)緩慢添加至燒瓶。於將H2NNMe2加至溶液的過程中觀察到白色沉澱物。於添加完成後,將混合物攪拌隔夜,過濾,及於真空中自濾液移除所有揮發物質。粗製產率為86%(54克,230毫莫耳)。使用真空蒸餾於純化終產物,其於35毫托爾下具有大約45℃之沸點。1H NMR(C6D6):δ 0.33(s,12H,-CH 3 Si);1.90(br,2H,-HN);2.27(s,12H,-CH 3 N)。13C{1H}NMR(C6D6):δ -0.68(-SiCH 3 );52.6(-NCH 3 )。質譜:m/z 175[M+ -(-HNNMe2)]、132[M+ -(-HNNMe2)-(-NMe2)]、116[M+ -(-SiMe2(HNNMe2))]。C8H26N4Si2:實測(計算),C:40.81%(40.98%),H:10.99%(11.18%),及N:23.67%(23.89%)。
圖2顯示Me4Si2(NHNMe2)2之STA圖,其在室溫下為液體且可完全以其之蒸氣形態輸送而於約350℃下有極少(<1%)殘留物質。利用質子NMR研究監測Me4Si2(HNNMe2)2於溶液中在100℃下之熱穩定性7天,而未偵測到顯著的分解。
實施例3 自Me4Si2(NHNMe2)2沉積碳氮化矽
製備實施例2之化合物(Me4Si2(NHNMe2)2)於烴溶劑中之0.40M濃度的溶液。以0.10毫升每分鐘(相當於約2
sccm)計量此溶液,以10 sccm之He作為遞送氣體,並於70℃下蒸發。將蒸氣與10 sccm之NH3混合於維持在100℃下之噴頭裝置中,因而分散於經加熱至550℃之Si(100)晶圓的表面上。在沉積過程中將室壓維持在1托爾下。薄膜係以1.3奈米/分鐘之速率沉積。
於此考慮使用作為前驅物溶劑之烴溶劑包括,但不限於,烷、烯、炔、環烷類、芳族化合物諸如苯及其衍生物、烷醇及胺。
使用RBS(廬瑟福後散射(Rutherford Backscattering))、HFS(氫前散射(Hydrogen Forward Scattering))、及NRA(核反應分析)技術之組合之薄膜的化學分析顯示薄膜組成物為22.9% Si、13.2% N、33.1% C、25.0% H及在632奈米下之折射率為1.98。
雖然本發明已參照各種特定具體例說明於文中,但當明瞭本發明並不因此而受限,而係可延伸至及涵蓋如可由熟悉技藝人士所明瞭之各種其他修改及具體例。因此,本發明係應根據隨後之申請專利範圍作廣義地解釋及詮釋。
圖1係Me2(NEt2)Si-Si(NEt2)Me2於Ar中之STA圖。
圖2係Me4Si2(NHNMe2)2於Ar中之STA圖。
Claims (17)
- 一種具下式結構之矽化合物:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x 其中:R1、R2及R3可彼此相同或不同,且各自係獨立地選自H、C1-C5烷基與C3-C6環烷基所構成之群組;及x係1或2。
- 如申請專利範圍第1項之矽化合物,其式為Me2(NEt2)Si-Si(NEt2)Me2、Me2(NEtMe)Si-Si(NEtMe)Me2及Me2(NMe2)Si-Si(NMe2)Me2,其中Me為甲基而Et為乙基。
- 一種具下式結構之矽化合物:
- 如申請專利範圍第3項之矽化合物,其式為(Me2NNMe)Me2Si-SiMe2(MeNNMe2),其中Me為甲基。
- 一種於一基板上形成一含矽薄膜之方法,包括使該基板於包括溫度低於600℃之化學氣相沉積條件下與一具下式結構的矽化合物之蒸氣接觸:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x 其中:R1、R2及R3可彼此相同或不同,且各自係獨立地選自H、C1-C5烷基與C3-C6環烷基所構成之群組;及x係1或2。
- 如申請專利範圍第5項之方法,其中該含矽薄膜包括一選自氧氮化矽、氮化矽、碳氮化矽及氧碳氮化矽所構成之群組的材料。
- 如申請專利範圍第5項之方法,其中該含矽薄膜包括一選自碳氮化矽及氧碳氮化矽所構成之群組的材料。
- 如申請專利範圍第5項之方法,其中該沉積條件包括低於約550℃之溫度。
- 一種於一基板上形成一含矽薄膜之方法,包括使該基板於包括溫度低於600℃之化學氣相沉積條件下與一具下式結構的矽化合物之蒸氣接觸:
- 如申請專利範圍第9項之方法,其中該含矽薄膜包括一選自氧氮化矽、氮化矽、碳氮化矽及氧碳氮化矽所構成之群組的材料。
- 如申請專利範圍第9項之方法,其中該含矽薄膜包括一選自碳氮化矽及氧碳氮化矽所構成之群組的材料。
- 如申請專利範圍第9項之方法,其中該沉積條件包括低於約550℃之溫度。
- 一種於一基板上形成一含矽薄膜之方法,包括使該基板於包括溫度低於600℃之化學氣相沉積條件下與一具下式結構的矽化合物之蒸氣接觸:
- 如申請專利範圍第13項之方法,其中該含矽薄膜包括一選自氧氮化矽及氮化矽薄膜所構成之群組的材料。
- 如申請專利範圍第13項之方法,其中該沉積條件包括低於約550℃之溫度。
- 一種製備具下式結構之矽化合物的方法:(R 2 R 3 N) 3-x R 1 x Si-SiR 1 x (NR 2 R 3 ) 3-x 其中:R1、R2、及R3可彼此相同或不同,且各自係獨立地選自H、C1-C5烷基與C3-C6環烷基所構成之群組;及x係1或2;該方法包括使一式XR1R2Si-SiXR1R2之二矽烷化合物與一二級胺類(R2R3NH)及一三級胺類(R1R2R3N)化合物反 應,其中X係選自溴、氟及氯所構成之群組,而R1、R2及R3係如前所述,其之反應係根據下式:XR1R2Si-SiXR1R2+R2R3NH+R1R2R3N → (R2R3N)3-xR1 xSi-SiR1 x(NR2R3)3-x。
- 一種於一基板上形成一矽薄膜或含矽薄膜之方法,包括使該基板接觸具下式結構之一矽化合物的一蒸氣,
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US8802882B2 (en) | 2014-08-12 |
US9783558B2 (en) | 2017-10-10 |
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TW200606169A (en) | 2006-02-16 |
US20150315215A1 (en) | 2015-11-05 |
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US9102693B2 (en) | 2015-08-11 |
US20050080286A1 (en) | 2005-04-14 |
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