TWI773002B - 用於沉積含矽膜的組合物及其方法 - Google Patents
用於沉積含矽膜的組合物及其方法 Download PDFInfo
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- TWI773002B TWI773002B TW109143007A TW109143007A TWI773002B TW I773002 B TWI773002 B TW I773002B TW 109143007 A TW109143007 A TW 109143007A TW 109143007 A TW109143007 A TW 109143007A TW I773002 B TWI773002 B TW I773002B
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- Prior art keywords
- plasma
- branched
- linear
- alkyl
- hydrogen
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 58
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010703 silicon Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 230000008021 deposition Effects 0.000 title description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 123
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 210000002381 plasma Anatomy 0.000 claims description 154
- 229910052739 hydrogen Inorganic materials 0.000 claims description 64
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 63
- 239000001257 hydrogen Substances 0.000 claims description 62
- 239000002243 precursor Substances 0.000 claims description 58
- 238000000151 deposition Methods 0.000 claims description 52
- 230000009969 flowable effect Effects 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 150000002431 hydrogen Chemical group 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
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- 239000001301 oxygen Substances 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 17
- 239000001307 helium Substances 0.000 claims description 17
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 17
- 238000012876 topography Methods 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
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- 239000000126 substance Substances 0.000 claims description 6
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- 238000011065 in-situ storage Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- LUXIMSHPDKSEDK-UHFFFAOYSA-N bis(disilanyl)silane Chemical class [SiH3][SiH2][SiH2][SiH2][SiH3] LUXIMSHPDKSEDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012707 chemical precursor Substances 0.000 claims description 2
- LICVGLCXGGVLPA-UHFFFAOYSA-N disilanyl(disilanylsilyl)silane Chemical class [SiH3][SiH2][SiH2][SiH2][SiH2][SiH3] LICVGLCXGGVLPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 12
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 1
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 16
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- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004541 SiN Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
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Abstract
於本文中描述出一種使用來在一具有表面構形的基材之至少一表面上形成一含矽膜的組合物及方法,其中該含矽膜有諸如但不限於碳化矽、氮化矽、氧化矽、氧氮化矽、摻雜碳的氮化矽、摻雜碳的氧化矽或摻雜碳的氧氮化矽膜。在一個態樣中,該含矽膜係使用共沈積一包含碳碳雙或碳碳三鍵的第一化合物與一包含至少一個Si-H鍵的第二化合物進行沈積。
Description
相關申請案之交互參照
本申請案主張2016年2月26日提出的申請案案號62/300,312之利益。該申請案案號62/300,312之揭示藉此以參考方式併入本文。
於本文中描述出一種用於電子裝置製造的方法。更特別是,於本文中描述出一種用於沈積製程以形成含矽膜之組合物,其中該沈積製程有諸如但不限於流動式化學氣相沈積法。可使用於本文中所描述的組合物及方法進行沈積之範例性含矽膜包括但不限於氧化矽、氮化矽、碳化矽、氧氮化矽或摻雜碳的氧化矽或摻雜碳的氮化矽膜。
美國早期公開案號2013/0217241揭示出含Si-C-N的可流動層之沈積及處理。該Si及C可來自含Si-C前驅物,同時該N可來自含N前驅物。對該初始含Si-C-N的可流動層進行處理以移除啟動該流動能力之組分。移除這些組分可增加蝕刻耐受性、減低收縮、調整膜張力及電性質。該後處理可係熱退火、UV曝光或高密度電漿。
美國專利案號8889566揭示出一種使用局部電漿激發該矽前驅物及使用第二電漿進行沈積來沈積可流動膜之方法。該矽前驅物可係矽烷胺、較高級數的矽烷或經鹵化的矽烷。該第二反應物氣體可係NH3
、N2
、H2
及/或O2
。
美國專利案號7825040揭示出一種藉由引進烷氧基矽烷或胺基矽烷前驅物來填充間隙,及藉由電漿反應沈積一可流動的含Si膜之方法。該前驅物不包括Si-C鍵或C-C鍵。
美國專利案號8889566、7521378及8575040描述出一種使用流動式化學氣相沈積製程來沈積氧化矽膜的方法,其係一種氣相聚合反應。使用諸如三矽烷胺(TSA)的化合物來沈積含Si、H及N寡聚物,其隨後使用臭氧曝露氧化成SiOx
膜。
美國專利案號8846536揭示出一種沈積及修改可流動的介電膜之方法。可藉由一或多種整合方法將該可流動的介電膜之溼蝕刻速率改變至少10倍因子。
先前認定的專利及專利申請案之揭示藉此以參考方式併入本文。
雖然技藝中近來的活動係與流動式化學氣相沈積法及其它膜沈積製程相關,但問題仍然存在。這些問題之一係與膜應力及空洞化相關。可流動膜大部分在較低溫度下進行沈積,高溫及高能量後處理會導致高膜應力及在構形中產生空洞。由於在低製程溫度下的膜品質低,此已經挑戰該溼蝕刻速率將會降低。因此,對提供可替代的前驅物化合物、前驅物組合或修改技術、或其組合有需求。
於本文中所描述的組合物或調配物及其使用方法係藉由在基材表面之至少一部分上沈積一含矽膜而克服先述技藝的問題,其在後沈積處理後提供想要的膜性質。本發明的組合物及方法可提供一種具有下列特徵之含矽膜:i)該膜在熱硬化後之抗張應力範圍係約10至約20 MPa,及在UV硬化後之範圍係約150至約190 MPa,如使用Toho應力工具測量;及ii)其密度範圍係約1.35至約2.10克/立方公分,如藉由X射線反射係數測量。
該含矽膜係選自於由下列所組成之群:氮化矽、碳化矽、氧化矽、摻雜碳的氮化矽、氧氮化矽及摻雜碳的氧氮化矽膜。在某些具體實例中,該基材包含一表面構形(surface feature)。如於本文所使用,用語”表面構形”意謂著該基材或部分製造的基材包含下列孔洞、溝槽、淺溝隔絕層(STI)、通道、回流(reentrant)構形或其類似構形之一或多種。該組合物可係預混合的組合物、預混合物(在使用於沈積製程前混合)或就地(in-situ)混合物(在沈積製程期間混合)。因此,在本揭示中,用語”混合物”、”調配物”及”組合物”可互換。
在一個態樣中,有提供一種用以沈積含矽膜的方法,該方法包括:
將一包含表面構形的基材放入一在-20℃至約400℃之範圍內的一或多種溫度下之反應器中;
將一具有至少一個碳碳雙鍵或碳碳三鍵的第一化合物引進該反應器中,其中該至少一種第一化合物具有式Rn
SiR1 4-n
,其中R係選自於線性或分枝的C2
至C6
烯基、線性或分枝的C2
至C6
炔基;R1
係選自於氫及分枝的C1
至C10
烷基;及n係選自於0、1、2、3的數字;
將一具有至少一個Si-H鍵的第二化合物引進該反應器中,其中該至少一種第二化合物係選自於由下列式IIA至IIH及IIIA所組成之群:
IIA. 具有式Six
H2x+2
的聚矽烷化合物,其中x係2至6的數字;
IIB. 具有式R1 m
SiH4-m
的化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;及m係選自於1、2及3的數字;
IIC. 具有式SiH3-
R2 -
SiH3
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;
IID. 具有式R3
SiH2-
R2 -
SiH2
R4
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIE. 具有式(R3
R4
N)n
SiH3-n
R1
的化合物,其中R1
係選自於氫及分枝的C1
至C10
烷基;R3
係選自於氫、分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIF. 矽雜環烷基化合物;
IIG. 三矽烷胺化合物或其衍生物;
IIH. 具有式[(R3
R4
N)p
SiH3-p
]2
NR1
或[R3 p
SiH2-p
NR1
]q
的矽氮烷化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;p=0、1、2;q=2或3;
IIIA. 具有式(R3
R4
N)SiH2
SiH3
的有機胺基二矽烷,其中R3
係選自於氫、分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;在某些具體實例中,R3
及R4
可連結形成環;在其它具體實例中,R3
及R4
未連結形成環;及
將一電漿來源提供進該反應器中以讓該第一與第二化合物至少部分反應而形成一可流動的液體或寡聚物,其中該可流動的液體或寡聚物至少部分填充該表面構形的一部分。
在一個特別具體實例中,該電漿來源係選自於由下列所組成之群,但不限於:氮電漿;包含氮及氦的電漿;包含氮及氬的電漿;氨電漿;包含氨及氦的電漿;包含氨及氬的電漿;氦電漿;氬電漿;氫電漿;包含氫及氦的電漿;包含氫及氬的電漿;包含氨及氫的電漿;有機胺電漿;包含氧的電漿;包含氧及氫的電漿;及其混合物。
在另一個具體實例中,該電漿來源係選自於由碳來源電漿所組成之群,但不限於,其包括烴電漿、包含烴及氦的電漿、包含烴及氬的電漿、二氧化碳電漿、一氧化碳電漿、包含烴及氫的電漿、包含烴及氮來源的電漿、包含烴及氧來源的電漿、及其混合物。
在上述之任何中或在任擇的具體實例中,於約100℃至約1000℃的範圍內之一或多種溫度下處理該可流動的液體或寡聚物以緻密化該材料之至少一部分。
在某些具體實例中,將該後熱處理材料曝露至電漿、紅外光、化學處理、電子束或UV光以形成一緻密的膜。
上述步驟定義出於本文中所描述的方法之一個循環,及可重覆該循環直到獲得想要厚度之含矽膜。在此或其它具體實例中,要了解可以多種順序進行、可相繼或同時地進行(例如,在另一個步驟的至少一部分期間)及其任何組合進行於本文中所描述的方法之步驟。可藉由變化該等化合物及其它試劑之供應時間週期來進行供應其的各別步驟,以便改變所產生的含矽膜之組合物的化學計量。
本發明的一個具體實例係關於一種用以形成含矽膜且包含至少二種化合物之化學前驅物,其中第一化合物包含至少一種選自於由具有至少一個碳碳雙鍵或C-C三鍵的化合物所組成之群的成員,其中該化合物係由式Rn
SiR1 4-n
表示,其中R係選自於線性或分枝的C2
至C6
烯基、線性或分枝的C2
至C6
炔基,R1
係選自於氫及分枝的C1
至C10
烷基,及n係選自於0、1、2及3的數字;及第二化合物包含至少一種選自於由下列式所組成之群的成員:
IIA. 具有式Six
H2x+2
的聚矽烷化合物,其中x係2至6的數字;
IIB. 具有式R1 m
SiH4-m
的化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基,及m係選自於1、2及3的數字;
IIC. 具有式SiH3-
R2 -
SiH3
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;
IID. 具有式R3
SiH2-
R2 -
SiH2
R4
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIE. 具有式(R3
R4
N)n
SiH3-n
R1
的化合物,其中R1
係選自於氫及分枝的C1
至C10
烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIF. 矽雜環烷基化合物;
IIG. 三矽烷胺化合物或其衍生物;
IIH. 具有式[(R3
R4
N)p
SiH3-p
]2
NR1
或[R3 p
SiH2-p
NR1
]q
的矽氮烷化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;p=0、1、2;q=2或3;及
IIIA. 具有式(R3
R4
N)SiH2
SiH3
的有機胺基二矽烷,其中R3
係選自於氫、分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;在某些具體實例中,R3
及R4
可連結形成環;在其它具體實例中,R3
及R4
未連結形成環。
本發明的另一個具體實例係關於一種藉由本發明的方法形成之膜和具有先前確認的特徵之膜。
本發明的多個具體實例可單獨或彼此組合著使用。
於本文中所描述的方法及化合物包含至少二種矽前驅物化合物:至少一種第一化合物及至少一種第二化合物。
於本文中描述出一種包含至少二種前驅物化合物的組合物;及使用其,經由化學氣相沈積(CVD)製程在具有表面構形的基材之至少一部分上沈積可流動膜的方法。藉由例如流動式化學沈積處理所沈積的膜會在後處理期間由於低製程溫度而遭遇到膜收縮。可由於明顯膜收縮及膜應力增加在膜中形成空洞及接縫。因此,已經對沒有增加膜應力或產生空洞但緻密化該膜進行挑戰。於本文中所描述的組合物及方法藉由使用共沈積至少二種前驅物化合物來改良在基材表面構形之至少一部分上的填充而克服這些問題。雖然不由理論界限,咸信可藉由使用包含不飽和碳鍵的第一化合物來產生交聯量增加,其中該不飽和碳鍵會斷裂及至少部分與具有至少一個Si-H鍵的第二化合物反應。該反應可在沈積步驟、處理步驟或沈積與處理步驟二者期間發生。因此,改良交聯可減少在處理步驟(例如,熱退火及/或UV硬化)期間於間隙填充中增加空洞。
於本文中所描述的方法及化合物包含至少二種矽前驅物化合物:至少一種具有不飽和碳鍵(例如,碳碳雙鍵或碳碳三鍵)的第一化合物及至少一種具有至少一個Si-H鍵的第二化合物。
該第一化合物係具有至少一個碳碳雙鍵或C-C三鍵的化合物,其中該化合物係由式Rn
SiR1 4-n
表示,其中R係選自於線性或分枝的C2
至C6
烯基、線性或分枝的C2
至C6
炔基;R1
係選自於氫及分枝的C1
至C10
烷基;及n係選自於0、1、2及3的數字。式I的範例性化合物包括但不限於下列:
該第二化合物係一種包含至少一個Si-H鍵的化合物及係至少一種選自於由下列式IIA至IIH及IIIA所組成之群的化合物:
IIA. 具有式Six
H2x+2
的聚矽烷化合物,其中x係2至6的數字;
IIB. 具有式R1 m
SiH4-m
的化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;及m係選自於1、2及3的數字;
IIC. 具有式SiH3-
R2 -
SiH3
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;
IID. 具有式R3
SiH2-
R2 -
SiH2
R4
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIE. 具有式(R3
R4
N)n
SiH3-n
R1
的化合物,其中R1
係選自於氫及分枝的C1
至C10
烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIF. 矽雜環烷基化合物;
IIG. 三矽烷胺化合物或其衍生物;
IIH. 具有式[(R3
R4
N)p
SiH3-p
]2
NR1
或[R3 p
SiH2-p
NR1
]q
的矽氮烷化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;p=0、1、2;q=2或3;
IIIA. 具有式(R3
R4
N)SiH2
SiH3
的有機胺基二矽烷,其中R3
係選自於氫、分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;在某些具體實例中,R3
及R4
可連結形成環;在其它具體實例中,R3
及R4
未連結形成環。
式IIA的範例性化合物包括但不限於二矽烷、三矽烷、四矽烷、五矽烷、六矽烷及其組合。
在上述式中及遍及本說明,用語”線性或分枝的烷基”指示為具有1至10、3至10、或1至6個碳原子的線性官能基。在上述式中及遍及本說明,用語”分枝的烷基”指示為具有3至10或1至6個碳原子的線性官能基。範例性線性或分枝的烷基包括但不限於甲基(Me)、乙基(Et)、異丙基(Pri
)、異丁基(Bui
)、二級丁基(Bus
)、三級丁基(But
)、異戊基、三級戊基(am)、異己基及新己基。在某些具體實例中,該烷基可接附有一或多個官能基,其係諸如但不限於烷氧基、二烷基胺基或其組合。在其它具體實例中,該烷基不接附有一或多個官能基。該烷基可係飽和,或任擇地,不飽和。
在上述式中及遍及本說明,用語”環烷基”指示為具有3至10或5至10個原子的環狀基團。範例性環烷基包括但不限於環丁基、環戊基、環己基及環辛基。在某些具體實例中,該環烷基可具有一或多個C1
至C10
線性、分枝的取代基;或包括氧或氮原子的取代基。在此或其它具體實例中,該環烷基可具有一或多個線性或分枝的烷基或烷氧基作為取代基,諸如例如,甲基環己基或甲氧基環己基。
在上述式中及遍及本說明,用語”芳基”指示為具有3至10個碳原子、5至10個碳原子或6至10個碳原子的芳香族環狀官能基。範例性芳基包括但不限於苯基、苄基、氯苄基、甲苯基及鄰-茬基。
在上述式中及遍及本說明,用語”烯基”指示為具有一或多個碳碳雙鍵且具有2至12、2至10、或2至6個碳原子的基團。範例性烯基包括但不限於乙烯基或烯丙基。
用語”炔基”指示為具有一或多個碳碳三鍵且具有2至12或2至6個碳原子的基團。
用語”伸烷基”指示為衍生自烷基藉由移除二個氫原子形成的基團。範例性伸烷基包括但不限於伸甲基(-CH2
-)或伸乙基(-CH2
CH2
-)。
在上述式中及遍及本說明,如於本文中所使用,用語”不飽和”意謂著該官能基、取代基、環或橋具有一或多個碳雙或三鍵。該不飽和環的實施例可係但不限於芳香環,諸如苯基環。用語”飽和”意謂著該官能基、取代基、環或橋不具有一或多個雙或三鍵。
在某些具體實例中,於式中之一或多個烷基、烯基、炔基、芳基及/或環烷基可”經取代”或具有一或多個經取代替代例如氫原子的原子或原子基團。範例性取代基包括但不限於氧、硫、鹵素原子(例如,F、Cl、I或Br)、氮、烷基及磷。在其它具體實例中,於式中之一或多個烷基、烯基、炔基、芳香族及/或芳基可未經取代。
本發明的第一及第二前驅物比率範圍可係約0:5至約2:1及其將以所選擇的第一及第二前驅物之函數變化。在本發明的一個態樣中,可使用增加TVS對TSA之比率來減少空洞化(或增加密度)。
可以多種方式將於本文中所描述的矽前驅物化合物傳遞至反應艙,諸如CVD或ALD反應器。在一個具體實例中,可使用液體傳遞系統。在任擇的具體實例中,可使用結合的液體傳遞及急驟蒸發製程單元,諸如例如,由MSP Corporation of Shoreview,MN製造的渦輪蒸發器,以便能夠體積傳遞低揮發性材料,其導致可再現性運輸及沈積而沒有前驅物熱分解。在液體傳遞調配物中,於本文中所描述的前驅物可以純淨的液體形式傳遞,或任擇地,可以溶劑調配物或包含其之組合物使用。因此,在某些具體實例中,該前驅物調配物可包括具有如可於所提供的末端使用應用中想要且優良之合適特徵的溶劑組分,以於基材上形成一膜。合適的溶劑之實施例可包含至少一種選自於由非極性烷烴基底的溶劑所組成之群的成員,諸如環己烷及環己酮。
該矽前驅物化合物較佳為實質上無鹵離子,諸如氯;或金屬離子,諸如Al。如於本文所使用,用語”實質上無”,當其係關於鹵離子(或鹵化物),諸如例如氯化物、氟化物、溴化物、碘化物;Al3+
離子、Fe2+
、Fe3+
、Ni2+
、Cr3+
時,其意謂著少於5 ppm(以重量計),較佳為少於3 ppm,及更佳為少於1 ppm及最佳為0 ppm。氯化物或金屬離子已知作用為矽前驅物的分解觸媒。在最後產物中明顯的氯化物程度可造成矽前驅物降解。矽前驅物逐漸降解可直接衝擊膜沈積製程,使得半導體製造者難以符合膜規格。此外,較高的矽前驅物降解速率會負面衝擊閑置壽命或穩定性,因此造成難以保證1-2年的閑置壽命。再者,已知矽前驅物會在分解後形成易燃及/或可自燃的氣體,諸如氫及矽烷。因此,矽前驅物之加速分解顯現出與形成這些易燃及/或可自燃的氣體副產物相關之安全性及性能的擔憂。
使用來形成於本文中所描述的膜或塗層之方法係流動式化學沈積製程。合適於本文中所揭示的方法之沈積製程的實施例包括但不限於循環式流動式化學氣相沈積法(CFCVD)或電漿輔助流動式化學氣相沈積法(PEFCVD)。如於本文中所使用,用語”流動式化學氣相沈積製程”指為如下的任何製程,其將基材曝露至一或多種揮發性前驅物,該前驅物會在基材表面上反應及/或分解以提供可流動的寡聚性含矽物種;然後,在進一步處理後產生該固體膜或材料,及在某些情況中,該寡聚性物種之至少一部分包含聚合物種。雖然於本文中所使用的前驅物、試劑及來源有時可描述為”氣體”,要了解該前驅物可係能經由直接蒸發、吹泡或昇華且以或不以惰性氣體運輸進反應器中的液體或固體。在某些情況中,該經蒸發的前驅物可通過電漿產生器。在一個具體實例中,該膜係使用電漿基礎(例如,遠程或就地產生)CVD方法進行沈積。如於本文中所使用,用語”反應器”包括但不限於反應艙或沈積艙。
可以多種方式將具有式I及IIA-H的化合物前驅物傳遞至流動式化學氣相沈積反應器,包括但不限於蒸氣引入(vapor draw)、吹泡或直接液體注入(DLI)。在一個具體實例中,可使用液體傳遞系統。在另一個具體實例中,該反應器可配備有雙腔(dual plenum)蓮蓬頭以將所產生的電漿物種保持成與前驅物蒸氣遠遠分開,直到它們在反應器中結合而沈積可流動的液體。在任擇的具體實例中,可使用結合的液體傳遞及急驟蒸發製程單元,諸如例如,由MSP Corporation of Shoreview,MN製造的渦輪蒸發器,以便能夠體積傳遞低揮發性材料,其導致可再現性運輸及沈積而沒有前驅物熱分解。在液體傳遞調配物中,於本文中所描述的前驅物可以純淨的液體形式傳遞,或任擇地,可以溶劑調配物或包含其的組合物使用。因此,在某些具體實例中,該前驅物調配物可包括在所提供的末端使用應用中具有如可想要且優良的合適特徵之溶劑組分,以在基材上形成一膜。在某些具體實例中,可將二種具有式I及IIA-H的前驅物傳遞至不同注入口以避免在進入反應器艙前於二種前驅物間進行反應。在另一個具體實例中,若它們相容時,可預混合二或更多種具有式I及IIA-H的前驅物,然後使用DLI方法將其傳遞進反應器艙中。
在某些具體實例中,可將該基材曝露至一或多種預沈積處理,諸如但不限於電漿處理、熱處理、化學處理、紫外光曝光、電子束曝光及其組合,以影響該膜的一或多種性質。可在選自於惰性、氧化及/或還原之環境下進行這些預沈積處理。
對該化合物、含氮來源、氧來源、其它前驅物或其組合之至少一種施加能量以在該基材上誘發反應及形成含矽膜或塗層。此能量可藉由下列提供,但不限於:熱、電漿、脈衝電漿、廻旋電漿(helicon plasma)、高密度電漿、誘導耦合電漿、X射線、電子束、光子、遠程電漿方法及其組合。在某些具體實例中,可使用二次RF頻率來源來修改在該基材表面處的電漿特徵。在該沈積包括電漿的具體實例中,該電漿產生方法可包括直接電漿產生方法,其直接在反應器中產生電漿;或任擇地遠程電漿產生方法,其在反應器外部產生電漿及將其供應進反應器中。
如先前提到,該方法在包含表面構形的基材表面之至少一部分上沈積一膜。將該基材放進反應器中及將該基材維持在約-20℃至約400℃的範圍內之一或多種溫度下。在一個特別的具體實例中,該基材之溫度係低於艙壁。將該基材溫度保持在溫度低於100℃,較佳為在溫度低於25℃及最佳為低於10℃及高於-20℃。
如先前提到,該基材包含一或多種表面構形。在一個特別的具體實例中,該表面構形的寬度具有寬度1微米或較少,或寬度500奈米或較少,或寬度50奈米或較少,或寬度10奈米。在此或其它具體實例中,若存在時,該表面構形的縱深比率(深度對寬度比率)係0.1:1或較大,或1:1或較大,或10:1或較大,或20:1或較大,或40:1或較大。該基材可係單晶矽晶圓、碳化矽晶圓、氧化鋁(藍寶石)晶圓、玻璃薄片、金屬箔、有機聚合物膜;或可係聚合物、玻璃、矽或金屬3維物件。該基材可以在技藝中熟知的多種材料進行塗佈,包括氧化矽、氮化矽、非晶相碳、氧碳化矽、氧氮化矽、碳化矽、砷化鎵、氮化鎵及其類似膜。這些塗層可完全被覆該基材、可在多種材料的多層中及可經部分蝕刻以曝露出材料的下面層。該表面亦可在其上面具有一光阻材料,其已經使用一圖案進行曝光及顯影而部分被覆該基材。
在本發明的一個態樣中,該基材包含至少一種選自於由Si、SiOx
、SiN、SiGe、SiOC及SiON所組成之群的成員。在本發明的另一個態樣中,可使用本發明的含矽膜作為硬遮罩及對光阻提供蝕刻選擇性。在本發明的進一步態樣中,本發明的含矽膜作用為在導電材料間之介電膜、作為在導電與其它介電質間之阻障物或作為在夾心式介電質內之膜。
在某些具體實例中,該反應器的壓力係低於大氣壓或750托耳(105
巴斯卡(pascals)(Pa))或較低,或100托耳(13332 Pa)或較低。在其它具體實例中,該反應器的壓力係維持在約0.1托耳(13 Pa)至約10托耳(1333 Pa)的範圍內。
在一個特別具體實例中,於約-20至約400℃,或-20至約100℃,或-20至約40℃的範圍內之一或多種溫度下進行該引進步驟,其中將至少一種化合物及電漿引進該反應器中。在這些或其它具體實例中,該基材包括一包含表面構形的半導體基材。該包含氮的電漿可選自於由下列所組成之群:氮電漿、氮/氫電漿、氮/氦電漿、氮/氬電漿、氨電漿、氨/氦電漿、氨/氬電漿、氨/氮電漿、NF3
、NF3
電漿、有機胺電漿及其混合物。該至少一種化合物與氮來源進行反應及在該表面構形及基材的至少一部分上形成氮化矽膜(其係非化學計量)或碳氮化矽膜。如於本文所使用,用語”有機胺”描述為一種具有至少一個氮原子的有機化合物。該有機胺之實施例有但不限於甲胺、乙胺、丙胺、異丙胺、三級丁胺、二級丁胺、三級戊胺、乙二胺、二甲胺、三甲胺、二乙胺、吡咯、2,6-二甲基哌啶、二正丙胺、二異丙胺、乙基甲基胺、N-甲基苯胺、吡啶及三乙胺。
在另一個具體實例中,該電漿來源係選自於由碳來源電漿所組成之群,但不限於,其包括烴電漿、包含烴及氦的電漿、包含烴及氬的電漿、二氧化碳電漿、一氧化碳電漿、包含烴及氫的電漿、包含烴及氮來源的電漿、包含烴及氧來源的電漿、及其混合物。該至少一種化合物與碳來源進行反應及在該表面構形與基材的至少一部分上形成碳化矽膜(其係非化學計量)、或碳氮化矽膜、或氧氮化矽膜、或氧碳化矽膜、或氧碳氮化矽膜。
在不同具體實例中,該電漿來源係選自於但不限於氫電漿、氦電漿、氬電漿、氙電漿及其混合物。該至少一種化合物與電漿進行反應及在該表面構形與基材的至少一部分上形成氮化矽膜、或碳化矽膜、或碳氮化矽膜。
在某些具體實例中,於沈積含矽膜後,該基材選擇性在足以使得該氮化矽膜形成氧化矽或氧氮化矽或摻雜碳的氧化矽膜之某些製程條件下以含氧來源進行處理。該含氧來源可選自於由下列所組成之群:水(H2
O)、氧(O2
)、氧電漿、臭氧(O3
)、NO、N2
O、一氧化碳(CO)、二氧化碳(CO2
)、N2
O電漿、一氧化碳(CO)電漿、二氧化碳(CO2
)電漿及其組合。
在某些具體實例中,於約100℃至約1000℃的範圍內之一或多種溫度下處理該可流動的液體或寡聚物以緻密化該材料之至少一部分。
在某些具體實例中,將該後熱處理材料曝露至電漿、紅外光、化學處理、電子束或UV光,以形成一緻密的膜。
上述步驟定義出於本文中所描述的方法之一個循環,及可重覆該循環直到獲得想要的厚度之含矽膜。在此或其它具體實例中,要了解可以多種順序進行、可相繼或同時地進行(例如,在另一個步驟的至少一部分期間)及其任何組合進行於本文中所描述的方法之步驟。可藉由變化該等化合物及其它試劑之供應時間週期來進行供應其的各別步驟以改變所產生的含矽膜之組合物的化學計量。
在一個態樣中,有提供一種用以沈積含矽膜的方法,該方法包括:
將一包含表面構形的基材放入在-20℃至約400℃之範圍內的一或多種溫度下之反應器中;
將至少一種具有至少一個碳碳雙鍵或碳碳三鍵的第一化合物引進該反應器中,其中該第一化合物具有式Rn
SiR1 4-n
,其中R係選自於線性或分枝的C2
至C6
烯基、線性或分枝的C2
至C6
炔基;R1
係選自於氫及線性或分枝的C1
至C10
烷基;及n係選自於0、1、2及3的數字;
將具有至少一個Si-H鍵的第二化合物引進該反應器中,其中該至少一種第二化合物係選自於由下列式IIA至IIH及III所組成之群:
IIA. 具有式Six
H2x+2
的聚矽烷化合物,其中x係2至6的數字;
IIB. 具有式R1 m
SiH4-m
的化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;及m係選自於1、2及3的數字;
IIC. 具有式SiH3-
R2 -
SiH3
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;
IID. 具有式R3
SiH2-
R2 -
SiH2
R4
的化合物,其中R2
係線性或分枝的C1
至C6
伸烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIE. 具有式(R3
R4
N)n
SiH3-n
R1
的化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;R3
係選自於氫、線性或分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;
IIF. 矽雜環烷基化合物;
IIG. 三矽烷胺化合物或其衍生物;及
IIH. 具有式[(R3
R4
N)p
SiH3-p
]2
NR1
或[R3 p
SiH2-p
NR1
]q
的矽氮烷化合物,其中R1
係選自於氫及線性或分枝的C1
至C10
烷基;R3
係選自於氫、分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基;p=0、1、2;q=2或3;及
IIIA. 具有式(R3
R4
N)SiH2
SiH3
的有機胺基二矽烷,其中R3
係選自於氫、分枝的C1
至C10
烷基及C4
至C10
芳基;及R4
係選自於線性或分枝的C1
至C10
烷基。
將一電漿來源提供進該反應器中以讓該第一與第二化合物至少部分進行反應以形成一可流動的液體或寡聚物,其中該可流動的液體或寡聚物至少部分填充該表面構形的一部分。上述步驟定義出於本文中所描述的方法之一個循環,及可重覆該循環直到獲得想要的厚度之含矽膜。在此或其它具體實例中,要了解可以多種順序進行、可相繼或同時地進行(例如,在另一個步驟的至少一部分期間)及其任何組合進行於本文中所描述的方法之步驟。可藉由變化該等化合物及其它試劑的供應時間週期來進行供應其之各別步驟以改變所產生的含矽膜之組合物的化學計量。
該含氮電漿可選自於由下列所組成之群:氮電漿、氮/氫電漿、氮/氦電漿、氮/氬電漿、氨電漿、氨/氦電漿、氨/氬電漿、氨/氮電漿、NF3
、NF3
電漿、有機胺電漿及其混合物。
在另一個具體實例中,該電漿來源係選自於由碳來源電漿所組成之群,但不限於,其包括烴電漿、包含烴及氦的電漿、包含烴及氬的電漿、二氧化碳電漿、一氧化碳電漿、包含烴及氫的電漿、包含烴及氮來源的電漿、包含烴及氧來源的電漿、及其混合物。
在上述之任何中或在任擇的具體實例中,該電漿來源係選自於但不限於氫電漿、氦電漿、氬電漿、氙電漿及其混合物。該至少一種化合物與電漿在該表面構形及基材的至少一部分上進行反應及形成氮化矽膜、或碳化矽膜、或碳氮化矽膜。
在某些具體實例中,於沈積含矽膜後,該基材選擇性在足以讓氮化矽膜形成氧化矽或氧氮化矽或摻雜碳的氧化矽膜之某些製程條件下以含氧來源進行處理。該含氧來源可選自於由下列所組成之群:水(H2
O)、氧(O2
)、氧電漿、臭氧(O3
)、NO、N2
O、一氧化碳(CO)、二氧化碳(CO2
)、N2
O電漿、一氧化碳(CO)電漿、二氧化碳(CO2
)電漿及其組合。
在上述之任何中或在任擇的具體實例中,於約100℃至約1000℃的範圍內之一或多種溫度下處理該可流動的液體或寡聚物以緻密化該材料之至少一部分。
在某些具體實例中,將該後熱處理材料曝露至電漿、紅外光、化學處理、電子束或UV光以形成一緻密的膜。在本發明的一個具體實例中,在排放乙烯及矽烷氣體副產物之條件下進行包含曝露至UV光曝光的後處理。
提供下列實施例以闡明本發明之某些具體實例及其應該不限制所附加的申請專利範圍之範圍。
實施例
在中電阻率(8-12Ω公分)單晶矽晶圓基材及Si圖案晶圓上沈積流動式化學氣相沈積(FCVD)膜。在某些實施例中,可將所產生的含矽膜或塗層曝露至預沈積處理,諸如但不限於電漿處理、熱處理、化學處理、紫外光曝光、紅外線曝光、電子束曝光及/或其它處理,以影響一或多種膜性質。
可在Applied Materials Precision 5000系統之經修改的FCVD艙中使用矽烷或TEOS製程成套配方進行沈積。該艙具有直接液體注入(DLI)傳遞能力。該前驅物係液體,其傳遞溫度係與前驅物沸點相依。為了沈積初始可流動的氮化物膜,典型的液體前驅物流速係100-5000毫克/分鐘,就地電漿功率密度係0.25-3.5瓦/平方公分,壓力係0.75-12托耳。為了緻密化如所沈積的可流動膜,在真空中,使用經修改的PECVD艙,於100~1000℃,較佳為300~400℃下對該膜進行熱退火及/或UV硬化。藉由SCI反射計或Woollam偏振光橢圓計,在632奈米下測量厚度及折射率(RI)。典型的膜厚度範圍係10至2000奈米。藉由Nicolet穿透式傅立葉(Fourier)轉換紅外線光譜(FTIR)工具來測量及分析該以矽為基礎的膜之鍵結性質及氫含量(Si-H、C-H及N-H)。使用X射線反射率(XRR)達成全部密度測量。進行X射線光電子光譜法(XPS)及二次離子質譜法(SIMS)分析來決定該膜的元素組合物。藉由截面掃描式電子顯微鏡(SEM),使用Hitachi S-4700系統,以2.0奈米的解析度觀察在圖形化晶圓上的流動能力及間隙填充效應。
使用實驗設計(DOE)方法進行流動式CVD沈積。該實驗設計包括:二種前驅物流係100至5000毫克/分鐘,較佳為500至2000毫克/分鐘;NH3
流係0 sccm至1000 sccm,較佳為0至500 sccm;壓力係0.75至12托耳,較佳為6至10托耳;RF功率(13.56 MHz)係50至1000瓦,較佳為100~500瓦;低頻率(LF)功率係0至100瓦;及沈積溫度範圍係-20至400℃,較佳為-20至40℃。
實施例1:使用四乙烯基矽烷(TVS,式I)與1,4-二矽雜丁烷(DSB,式IID)沈積可流動的碳化矽膜
在實驗中,使用來沈積具有最適合的膜性質之可流動的碳化矽(SiC)膜之製程條件如下:功率=150瓦,間隔=250密耳,壓力=8托耳,溫度=35~40℃,TVS=500毫克/分鐘,1,4-二矽雜丁烷=750毫克/分鐘,He=200 sccm。在300℃下熱退火該可流動膜5分鐘,接著為400℃的UV硬化1、3、5及10分鐘。折射率及膜密度隨著UV處理時間而增加。截面SEM指示出藉由共沈積前驅物化合物TVS與1,4-二矽雜丁烷達成由下而上無縫及無空洞的間隙填滿,如顯示在圖1(a)及圖1(b)中。在300℃下熱退火該膜5分鐘及在400℃下UV硬化1分鐘。該可流動的SiC膜藉由周圍曝露顯示出好的穩定性。藉由偵測膜厚度變化(例如,如藉由折射率測量)來測量穩定性,其中具有差的穩定性之膜具有當曝露至周圍濕氣及氧程度時會被氧化而減少厚度。其在厚度或折射率上無變化。
實施例2:使用四乙烯基矽烷(TVS,式I)與三矽烷胺(TSA,式IIG)沈積可流動的碳氮化矽膜
在此實驗中,使用來沈積具有最適合的膜性質之可流動的碳氮化矽(SiCN)膜之製程條件如下:功率=200瓦,間隔=300密耳,壓力=6托耳,溫度=30℃,TVS=1700毫克/分鐘,TSA=1000毫克/分鐘,He=200 sccm,NH3
=450 sccm。在300℃下熱退火該可流動膜5分鐘,接著為400℃之UV硬化1、3、5及10分鐘。折射率及膜密度隨著UV時間而增加。截面SEM指示出藉由共沈積第一前驅物TVS與第二前驅物TSA達成由下而上無縫及無空洞的間隙填滿,如顯示在圖2(a)及圖2(b)中。在300℃下熱退火該膜5分鐘及在400℃下UV硬化10分鐘。該可流動的SiCN膜藉由周圍曝露顯示出好的穩定性。在厚度或折射率上無變化。亦藉由將該膜浸泡進稀HF溶液中測試WER。該可流動的SiCN膜顯示出耐HF溶液蝕刻性。
實施例3:使用四乙烯基矽烷(TVS,式I)與三矽烷胺(TSA,式IIG),藉由循環製程沈積可流動的碳氮化矽膜
此實驗使用在實施例2中的沈積條件。該沈積時間從10秒減少至1.5秒。圖3(a)~3(c)顯示出在1、2及3個循環加工後之間隙填滿效應。在每個循環中,沈積該膜,於300℃下熱退火5分鐘及於400℃下UV硬化10分鐘。一個加工循環可填充80~90%的間隙,如顯示在圖3(a)中。藉由3個加工循環間隙完全填滿及開始在結構頂端上生長膜層。
實施例4:使用四乙烯基矽烷(TVS,式I)與二異丙基胺基矽烷(DIPAS,式IIE)沈積可流動的碳氮化矽膜
在此實驗中,共沈積TVS與DIPAS形成可流動的SiCN膜。適合的沈積條件包括:功率=200~400瓦,間隔=300密耳,壓力=6托耳,溫度=25~30℃,TVS=1000毫克/分鐘,DIPAS=1000~1500毫克/分鐘,He=200 sccm,NH3
=450~1000 sccm。在這些條件下沈積溼且可流動的膜。然後,在300℃下熱退火該膜5分鐘。截面SEM指示出藉由共沈積第一前驅物TVS與第二前驅物DIPAS達成由下而上無縫及無空洞的間隙填滿,如顯示在圖4中。
實施例5:使用三乙烯基甲基矽烷(TVMS,式I)與三矽烷胺(TSA,式IIG)沈積可流動的碳氮化矽膜
在此實驗中,共沈積TVMS與TSA形成可流動的SiCN膜。適合的沈積條件包括:功率=200瓦,間隔=300密耳,壓力=6托耳,溫度=25~30℃,TSA=1000毫克/分鐘,TVMS=1000~1500毫克/分鐘,He=200 sccm,NH3
=600~1200 sccm。在這些條件下沈積溼且可流動的膜。然後,在300℃下熱退火該膜5分鐘及在400℃下UV硬化10分鐘。截面SEM指示出藉由共沈積第一前驅物TVMS與第二前驅物TSA達成由下而上無縫及無空洞的間隙填滿,如顯示在圖5中。以在TVMS中的甲基置換在TVS中的乙烯基不失去流動能力或間隙填滿結果。但是,藉由TVMS與TSA沈積的膜沒有形成交聯,其具有比藉由TVS+TSA低的密度。
實施例6:使用三乙烯基甲基矽烷(TVMS,式I)與1,4-二矽雜丁烷(DSB,式IIC)沈積可流動的碳氮化矽膜
在此實驗中,共沈積TVMS與DSB形成可流動的SiC膜。適合的沈積條件包括:功率=200~400瓦,間隔=300密耳,壓力=6托耳,溫度=25~30℃,DSB=1000毫克/分鐘,TVMS=1000~1500毫克/分鐘,He=200 sccm,NH3
=600~1200 sccm。在這些條件下沈積溼且可流動的膜。然後,在300℃下熱退火該膜5分鐘。截面SEM指示出藉由共沈積第一前驅物TVMS與第二前驅物DSB達成由下而上無縫及無空洞的間隙填滿,如顯示在圖6中。
實施例7:使用四乙烯基矽烷(TVS,式I)與N,N’-二矽烷基三矽氮烷(式IIG)沈積可流動的碳氮化矽膜
在此實驗中,共沈積TVS與TSA二聚物形成可流動的SiCN膜。適合的沈積條件包括:功率=150~300瓦,間隔=200~400密耳,壓力=6托耳,溫度=25~30℃,TSA二聚物=1000~1500毫克/分鐘,TVS=900~1300毫克/分鐘,He=200 sccm,NH3
=600~1200 sccm。在這些條件下沈積溼且可流動的膜。然後,在300℃下熱退火該膜5分鐘及在400℃下UV硬化10分鐘。截面SEM指示出藉由共沈積第一前驅物TVS與第二前驅物TSA二聚物達成由下而上無縫及無空洞的間隙填滿,如顯示在圖7中。與TVS及TSA組合比較,TVS及TSA二聚物組合闡明較高的膜密度(>1.8克/立方公分),較高的N含量(18~19%)及較低的C含量(36~37%)。
實施例8:使用四乙烯基矽烷(TVS,式I)與二異丙基胺基二矽烷(DIPADS,式IIIA)沈積可流動的碳氮化矽膜
在此實驗中,共沈積TVS與DIPADS形成可流動的SiCN膜。適合的沈積條件包括:功率=200~400瓦,間隔=300密耳,壓力=6托耳,溫度=25~30℃,TVS=1000~1500毫克/分鐘,DIPADS=1000~1500毫克/分鐘,He=200 sccm,NH3
=500~1000 sccm。在這些條件下沈積溼且可流動的膜。然後,在300℃下熱退火該膜5分鐘及在400℃下UV硬化10分鐘。截面SEM指示出藉由共沈積第一前驅物TVS與第二前驅物DIPADS達成由下而上無縫及無空洞的間隙填滿。
雖然上述已經與態樣或具體實例連結描述出本發明的某些原理,要清楚了解的是,此描述僅係以實施例說明之及不作為本發明的範圍之限制。
圖1(a)及圖1(b)顯示出藉由四乙烯基矽烷(TVS)與1,4-二矽雜丁烷形成之可流動的SiC膜之SEM截面影像,如在實施例1中所描述般。其闡明在後處理後,由下而上無縫及無空洞之間隙填滿。
圖2(a)及圖2(b)顯示出藉由四乙烯基矽烷(TVS)與三矽烷胺(TSA) 形成之可流動的SiC膜之SEM截面影像,如在實施例2中所描述般。其闡明在後處理後,由下而上無縫及無空洞之間隙填滿。
圖3(a)~(c)顯示出1、2及3個加工循環之SEM截面影像,如在實施例3中所描述般。其闡明一個循環製程填充該等間隙。
圖4顯示出SEM截面,其指示出藉由共沈積第一前驅物四乙烯基矽烷(TVS)與第二前驅物二異丙基胺基矽烷(DIPAS)達成由下而上無縫及無空洞的間隙填滿,如在實施例4中所描述般。
圖5顯示出SEM截面,其指示出藉由共沈積第一前驅物三乙烯基甲基矽烷(TVMS)與第二前驅物三矽烷胺(TSA)達成由下而上無縫及無空洞的間隙填滿,如在實施例5中所描述般。
圖6顯示出SEM截面,其指示出藉由共沈積第一前驅物三乙烯基甲基矽烷(TVMS)與第二前驅物1,4-二矽雜丁烷(DSB)達成由下而上無縫及無空洞的間隙填滿,如在實施例6中所描述般。
圖7顯示出SEM截面,其指示出藉由共沈積第一前驅物四乙烯基矽烷(TVS)與第二前驅物N,N’-二矽烷基三矽氮烷達成由下而上無縫及無空洞的間隙填滿,如在實施例7中所描述般。
Claims (22)
- 一種使用流動式化學氣相沈積製程來沈積含矽膜的方法,該方法包括:將一包含表面構形的基材放入一在-20℃至400℃之範圍內的一或多種溫度下之反應器中;將一選自於由下列所組成之群的第一化合物引進該反應器中: 及;及將一具有至少一個Si-H鍵的第二化合物引進該反應器中,其中該至少一種第二化合物係選自於由下列式IIA至IIH所組成之群:IIA.具有式SixH2x+2的聚矽烷化合物,其中x係2至6的數字;IIB.具有式R1 mSiH4-m的化合物,其中R1係選自於氫及線性或分枝的C1至C10烷基;及m係選自於1、2及3的數字;IIC.具有式SiH3-R2 -SiH3的化合物,其中R2係線性或分枝的C1至C6伸烷基;IID.具有式R3SiH2-R2 -SiH2R4的化合物,其中R2係線性或分枝的C1至C6伸烷基;R3係選自於氫、線性或分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;IIE.具有式(R3R4N)nSiH3-nR1的化合物,其中R1係選自於氫及線性或分枝的C1至C10烷基;R3係選自於氫、線性或分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;IIF.矽雜環烷基化合物; IIG.三矽烷胺化合物或其衍生物;及IIH.具有式[(R3R4N)pSiH3-p]2NR1或[R3 pSiH2-pNR1]q的矽氮烷化合物,其中R1係選自於氫及線性或分枝的C1至C10烷基;R3係選自於氫、線性或分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;p=0、1、2;q=2或3;及IIIA.具有式(R3R4N)SiH2SiH3的有機胺基二矽烷,其中R3係選自於氫、分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;將一電漿來源提供進該反應器中以讓該第一與第二化合物至少部分反應而形成一可流動的液體或寡聚物。
- 如請求項1之方法,其中該提供步驟包括一含氮電漿來源,其係選自於由下列所組成之群:氮電漿、包含氮及氫的電漿、包含氮及氦的電漿、包含氮及氬的電漿、氨電漿、包含氨及氦的電漿、包含氨及氬的電漿、包含氨及氮的電漿、NF3、NF3電漿、有機胺電漿及其混合物。
- 如請求項1之方法,其中該提供步驟包含一選自於由碳來源電漿所組成之群的電漿來源,其包括烴電漿、包含烴及氦的電漿、包含烴及氬的電漿、二氧化碳電漿、一氧化碳電漿、包含烴及氫的電漿、包含烴及氮來源的電漿、包含烴及氧來源的電漿及其混合物。
- 如請求項1之方法,其中該電漿來源係選自於氫電漿、氦電漿、氬電漿、氙電漿及其混合物。
- 如請求項1之方法,其中該提供步驟包括一含氧電漿來源,其係選自於由下列所組成之群:水(H2O)電漿、氧電漿、臭氧(O3)電漿、NO電漿、N2O電漿、一氧化碳(CO)電漿、二氧化碳(CO2)電漿及其組合。
- 如請求項1之方法,更包含在100℃至1000℃的範圍內之一或多種溫度下處理該可流動的液體或寡聚物,以緻密化該可流動的液體或寡聚物的至少一部份。
- 如請求項6之方法,其進一步進行包含選自於由下列所組成之群的至少一後熱處理以形成一緻密的膜:電漿、紅外光、化學處理、電子束及UV光。
- 如請求項1之方法,其中該沈積製程係一種電漿輔助化學氣相沈積法及該電漿係就地產生。
- 如請求項1之方法,其中該沈積製程係一種電漿輔助化學氣相沈積法及該電漿係遠程產生。
- 如請求項1之方法,其中該反應器的壓力係維持在100托耳或較低。
- 如請求項1之方法,其中該含矽膜係選自於由下列所組成之群:碳化矽、氮化矽、氧化矽、摻雜碳的氮化矽、摻雜碳的氧化矽、氧氮化矽及摻雜碳的氧氮化矽膜。
- 一種用以形成含矽膜而包含至少二種化合物的化學前驅物,其中第一化合物係選自於由下列所組成之群:及;及第二化合物包含至少一種選自於由下列式所組成之群的成員:IIA.具有式SixH2x+2的聚矽烷化合物,其中x係2至6的數字;IIB.具有式R1 mSiH4-m的化合物,其中R1係選自於氫及線性或分枝的C1至C10烷基;及m係選自於1、2及3的數字;IIC.具有式SiH3-R2 -SiH3的化合物,其中R2係線性或分枝的C1至C6伸烷基;IID.具有式R3SiH2-R2 -SiH2R4的化合物,其中R2係線性或分枝的C1至C6伸烷基;R3係選自於氫、線性或分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;IIE.具有式(R3R4N)nSiH3-nR1的化合物,其中R1係選自於氫及分枝的C1至C10烷基;R3係選自於氫、線性或分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;IIF.矽雜環烷基化合物;IIG.三矽烷胺化合物或其衍生物;IIH.具有式[(R3R4N)pSiH3-p]2NR1或[R3 pSiH2-pNR1]q的矽氮烷化合物,其中R1係選自於氫及線性或分枝的C1至C10烷基;R3係選自於氫、線性或分枝的C1 至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基;p=0、1、2;q=2或3;及IIIA.具有式(R3R4N)SiH2SiH3的有機胺基二矽烷,其中R3係選自於氫、分枝的C1至C10烷基及C4至C10芳基;及R4係選自於線性或分枝的C1至C10烷基。
- 如請求項12之前驅物,其中該第一化合物包含四乙烯基矽烷。
- 如請求項12之前驅物,其中該第二化合物包含至少一種選自於由下列所組成之群的成員:二矽烷、三矽烷、四矽烷、五矽烷、六矽烷及其組合。
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