JP2021061414A - 低温でのSiNの蒸着用Si前駆体 - Google Patents
低温でのSiNの蒸着用Si前駆体 Download PDFInfo
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- JP2021061414A JP2021061414A JP2020206502A JP2020206502A JP2021061414A JP 2021061414 A JP2021061414 A JP 2021061414A JP 2020206502 A JP2020206502 A JP 2020206502A JP 2020206502 A JP2020206502 A JP 2020206502A JP 2021061414 A JP2021061414 A JP 2021061414A
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- Prior art keywords
- silicon
- silicon nitride
- precursor
- sii
- thin film
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- 239000002243 precursor Substances 0.000 title claims abstract description 125
- 230000008021 deposition Effects 0.000 title abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 181
- 239000000376 reactant Substances 0.000 claims abstract description 150
- 238000000034 method Methods 0.000 claims abstract description 143
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 130
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000010408 film Substances 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 239000000758 substrate Substances 0.000 claims abstract description 108
- 239000012686 silicon precursor Substances 0.000 claims abstract description 107
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 95
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 84
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000010703 silicon Substances 0.000 claims abstract description 83
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 82
- 239000010409 thin film Substances 0.000 claims abstract description 69
- 238000000151 deposition Methods 0.000 claims abstract description 42
- 239000006227 byproduct Substances 0.000 claims abstract description 30
- 230000000694 effects Effects 0.000 claims abstract description 20
- 239000012808 vapor phase Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 229910052740 iodine Inorganic materials 0.000 claims description 54
- 238000005530 etching Methods 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 40
- 238000010926 purge Methods 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052794 bromium Inorganic materials 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 27
- 230000007246 mechanism Effects 0.000 claims description 25
- 238000007740 vapor deposition Methods 0.000 claims description 25
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 24
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 23
- 239000011630 iodine Substances 0.000 claims description 21
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001039 wet etching Methods 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 3
- 238000000465 moulding Methods 0.000 claims 1
- 210000002381 plasma Anatomy 0.000 description 70
- 239000012071 phase Substances 0.000 description 46
- 239000003446 ligand Substances 0.000 description 38
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 32
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 32
- 229910052736 halogen Inorganic materials 0.000 description 25
- 150000002367 halogens Chemical class 0.000 description 25
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 23
- 241000894007 species Species 0.000 description 23
- -1 hydrogen radicals Chemical class 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- 150000003973 alkyl amines Chemical class 0.000 description 20
- 235000013675 iodine Nutrition 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 15
- 239000012159 carrier gas Substances 0.000 description 12
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 12
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- 150000004703 alkoxides Chemical class 0.000 description 11
- 229910052734 helium Inorganic materials 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 239000013110 organic ligand Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- 125000006850 spacer group Chemical group 0.000 description 8
- 150000001923 cyclic compounds Chemical class 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 150000003377 silicon compounds Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- VQPFDLRNOCQMSN-UHFFFAOYSA-N bromosilane Chemical class Br[SiH3] VQPFDLRNOCQMSN-UHFFFAOYSA-N 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002052 molecular layer Substances 0.000 description 5
- 238000010923 batch production Methods 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical class I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 241000233805 Phoenix Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000000624 total reflection X-ray fluorescence spectroscopy Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- RNRZLEZABHZRSX-UHFFFAOYSA-N diiodosilicon Chemical compound I[Si]I RNRZLEZABHZRSX-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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- 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
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- 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
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- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
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- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L29/66409—Unipolar field-effect transistors
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- H01L29/66787—Unipolar field-effect transistors with an insulated gate, i.e. MISFET with a gate at the side of the channel
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Abstract
Description
(1)ケイ素前駆体が、基板表面上に吸着されるように、基板をケイ素前駆体と接触させる工程210、
(2)基板を窒素前駆体と接触させる工程220、ならびに
(3)所望の厚さおよび組成物の薄膜を得るために、必要に応じて何回でも工程210および200を繰り返す工程、を含む。
いくつかの実施形態において、プラズマ増幅ALD(PEALD)プロセスは、SiN膜を蒸着するために用いられる。要するに、基板またはワークピースは、反応チャンバーに配置され、交互の繰り返し表面反応を受ける。いくつかの実施形態において、SiN薄膜は、自己制御的なALDサイクルの繰り返しにより形成される。好ましくは、SiN膜を形成するため、各ALDサイクルは、少なくとも2つの異なる相を含む。反応空間からの反応物質の供給および反応空間からの反応物質の除去は、相を考えられてよい。第一相において、ケイ素を含む第一反応物質は、提供され、そして基板表面にわずかに約1つの単層を形成する。この反応物質は、本願明細書において、「ケイ素前駆体」、「ケイ素含有前駆体」、または「ケイ素反応物質」とも称され、例えばH2SiI2であってよい。
いくつかの好適なケイ素前駆体は、現在開示されているPEALDプロセスに用いられうる。少なくともいくつかの好適な前駆体は、以下の一般式であってよい。
上で論じたように本発明のPEALDプロセスにおける第二反応物質は、反応種を含んでよい窒素前駆体を含んでよい。好適なプラズマ組成物は、1つの形態または別の形態において窒素プラズマ、窒素ラジカル、または原子窒素を包含する。1つの形態または別の形態において、水素プラズマ、水素ラジカル、または原子水素も提供される。いくつかの実施形態において、プラズマは、希ガス(He、Ne、Ar、KrおよびXe、好ましくはArまたはHe)をプラズマ形態で、ラジカルとして、または原子形態で含有されてもよい。いくつかの実施形態において、第二反応物質は希ガス(Arなど)由来のいずれの種も含まない。したがって、いくつかの実施形態において、プラズマは、希ガスを含む気体中で発生されない。
(1)ケイ素化合物が基板表面上に吸着するように、基板を蒸発されたケイ素前駆体310と接触する工程、
(2)反応空間320に窒素前駆体を導入する工程、
(3)窒素前駆体330から反応種を生成する工程、および
(4)基板を反応種と接触させる工程340であって、これにより吸着されたケイ素化合物を窒化ケイ素に変換する工程。
(1)三次元構造を含む基板は、反応空間に提供される工程、
(2)ケイ素含有前駆体(SiI2H2など)は、ケイ素含有前駆体が基板の表面に吸着される反応空間に導入される工程、
(3)過剰のケイ素含有前駆体および反応副生成物は、反応空間から除去される工程、
(4)窒素含有前駆体(N2、NH3、N2H4、またはN2およびH2など)は反応空間に導入される工程、
(5)窒素前駆体から反応種を生成する工程、
(6)基板を反応種と接触させる工程、および
(7)過剰の窒素原子、プラズマ、またはラジカルおよび反応副生成物を除去する工程。
本発明で提供される方法は、熱的ALDプロセスにより、基板表面上への窒化ケイ素フィルムの蒸着も可能とする。三次元構造など幾何学的に困難な利用は、これらの熱的プロセスで可能でもある。いくつかの実施形態によれば、熱的原子層堆積(ALD)型プロセスは、集積回路ワークピースなどの基板上に窒化ケイ素フィルムを形成するために用いられる。
いくつかの好適なケイ素前駆体は、現在開示されている熱的プロセス(熱的ALDプロセスなど)に用いられてよい。いくつかの実施形態において、これらの前駆体は、所望の性質(所望のWER、WERR、パターン負荷効果または/およびステップカバレッジ、以下に記載されている機構のうちの少なくとも1つ)をフィルムが蒸着されるプラズマALDプロセスにおいて用いられてもよい。
窒素を含有するいくつかの好適なケイ素前駆体(ヨウ素または臭素置換シラザンなど)または硫黄を含有するいくつかの好適なケイ素前駆体は、現在開示されている熱的かつプラズマALDプロセスにおいて用いられてよい。いくつかの実施形態において、窒素を含有するケイ素前駆体(ヨウ素または臭素置換シラザンなど)は、所望の性質(例えば、所望のWER、WERR、パターン負荷効果または/および以下に記載されている機構のステップカバレッジのうちの少なくとも1つ)を有するフィルムが蒸着されている現在開示されている熱的かつプラズマALDプロセスにおいて用いられてよい。
いくつかの実施形態によれば、熱的ALDプロセスにおける第二反応物質または窒素前駆体はNH3、N2H4、またはNH3、N2H4、またはN−H結合を有する他の好適な窒素化合物の数であってよい。
(1)ケイ素化合物が基板表面上に吸着するように蒸発されたケイ素前駆体410を基板に接触させる工程、
(2)過剰のケイ素反応物質および任意の副生成物420を除去する工程、
(3)基板を窒素前駆体430と接触させる工程、ならびに
(4)過剰の窒素前駆体および反応副生成物440を除去する工程。
(1)反応空間に充填される基板、
(2)ケイ素含有前駆体(H2SiI2など)は、ケイ素含有前駆体が基板の表面に吸着されるように反応空間に導入される、
(3)過剰のケイ素含有前駆体および反応副生成物を除去する工程はパージする工程などにより除去される、
(4)窒素含有前駆体(NH3またはN2H4など)は反応空間に導入され、基板上でケイ素含有前駆体と反応する、
(5)パージするなどにより、過剰の窒素含有前駆体および反応副生成物を除去する工程、および
(6)段階(2)〜(5)が、所望の厚さの窒化ケイ素フィルムが形成されるまで繰り返されてよい。
本願明細書で論じられる実施形態のいくつかにより蒸着される窒化ケイ素薄膜(ケイ素前駆体が臭素またはヨウ素を含有しているかどうかに関わりなく)は、約3at−%未満、好ましくは約1at−%未満、より好ましくは約0.5at−%未満、最も好ましくは、約0.1at−%未満の不純物レベルまたは濃度を達成するかもしれない。ある薄膜において、水素を除く全不純物レベルは約5at−%未満、好ましくは約2at−%未満、より好ましくは約1at−%未満、最も好ましくは、約0.2at−%未満であってよい。そして、ある薄膜において、水素レベルは約30at−%未満、好ましくは約20at−%未満、より好ましくは約15at−%未満、最も好ましくは、約10at−%未満であってよい。
本願明細書に記載される方法および物質は向上した性質を有するフィルムを提供し得、改善されたエッチング特性は、水平ソース/ドレイン(S/D)およびゲート表面を有する伝統的な側部のトランジスタデザインだけでなく、非水平(例えば、垂直)表面および複雑な三次元(3D)構造に用いられるe改善されたSiNフィルムも提供もし得る。ある実施形態において、SiN膜は、集積回路製作中に三次元構造上に開示された方法により蒸着される。三次元トランジスタは、例えば、二重ゲート電界効果トランジスタ(DG FET)、およびFinFETを包含している他の型の多点ゲートFETを包含するかもしれない。例えば、本発明の窒化ケイ素薄膜は、非平面多点ゲートトランジスタ(FinFETなど)において有用であり得、ゲート、ソース、およびドレイン領域の最上部に加えて垂直な壁上にケイ化物を形成するのも望ましいかもしれない。
シラン前駆体としてH2SiI2および窒素前駆体としてH2+N2プラズマを用いるPEALDプロセスによる本願明細書の記載に基づき、窒化ケイ素薄膜を400℃で蒸着した。このフィルムは、ALD反応型(典型的な高品質のPEALD SiN膜)と熱ALDフィルムの等方性のエッチング態様と両方の最高の性質のいくつかの組み合わせを示した。しかしこれらの結果は完全には理解されず、フィルム特性およびエッチング態様は、それにもかかわらず高品質スペーサ層用途のスペックにあった。
改善されたエッチング特性および不純物含有量を含む窒化ケイ素薄膜(実施例1との比較)を、直流プラズマALDシャワーヘッド反応器中、本発明のPEALDプロセスにより蒸着した。200℃および400℃のサセプタ温度を用いた。H2SiI2をケイ素前駆体として用い、H2+N2プラズマを窒素前駆体として用いた。プラズマ出力は約200W〜約220Wであり、シャワーヘッドプレートおよびサセプタの間の空間(すなわち、プラズマが発生する空間)は、10mmだった。プラズマはArを含有していなかった。窒素をキャリアガスとして用い、蒸着プロセスの全体にわたって流した。H2SiI2消費は約9.0mg/サイクルだった。
Claims (36)
- (a)ケイ素前駆体が基板の表面に吸着されるように反応空間に気相のケイ素反応物質を導入する工程、
(b)過剰のケイ素反応物質および反応副生成物を除去する工程、
(c)吸着された前記ケイ素前駆体を窒素前駆体からのプラズマにより生成される反応種と接触させる工程、
(d)過剰の反応種および反応副生成物を除去する工程、
を含み、
ここで、工程(a)〜(d)が所望の厚さの窒化ケイ素フィルムが形成されるまで繰り返され、ならびに前記ケイ素反応物質がヨウ素または臭素を含む、
反応空間における基板上への窒化ケイ素薄膜の蒸着方法。 - 前記ケイ素反応物質が式(1)〜(8)の1つの式を有する前駆体を含む、請求項1に記載の蒸着方法。
- 前記反応種が、水素、水素原子、水素プラズマ、水素ラジカル、N*ラジカル、NH*ラジカルまたはNH2*ラジカルを含む、請求項1に記載の蒸着方法。
- 前記反応種が前記基板上に直接発生される、請求項1に記載の蒸着方法。
- 前記反応種が前記基板から離れて発生される、請求項1に記載の蒸着方法。
- 遠隔プラズマ発生器が、前記反応種を発生するために用いられる、請求項5に記載の方法。
- 前記ケイ素反応物質が、HSiI3、H2SiI2、H3SiI、H2Si2I4、H4Si2I2、およびH5Si2Iからなる群から選択される、請求項1に記載の蒸着方法。
- 前記ケイ素反応物質がH2SiI2である、請求項7に記載の方法。
- 約300℃〜約400℃の温度で行われる、請求項1に記載の蒸着方法。
- 前記窒素前駆体が、NH3、N2H4、N2/H2の混合物、N2、およびこれらの任意の混合物からなる群から選択される、請求項1に記載の蒸着方法。
- 前記窒化ケイ素薄膜が、少なくとも約80%のステップカバレッジおよびパターン負荷効果を示す、請求項1に記載の蒸着方法。
- 前記窒化ケイ素薄膜が三次元構造上に形成される、請求項1に記載の蒸着方法。
- 前記三次元構造が、側壁および最上部領域を含み、ならびに、前記最上部領域のウェットエッチング速度(WER)に対する前記窒化ケイ素フィルムの側面のWERが、0.5%dHF中、約3未満である、請求項12に記載の方法。
- 前記窒化ケイ素薄膜のエッチング速度が0.5%のHF水溶液中約4nm/分未満である、請求項1に記載の蒸着方法。
- 前記窒化ケイ素薄膜がFinFETの成形の間に蒸着される、請求項1に記載の蒸着方法。
- 前記吸着されたケイ素前駆体がArのプラズマにより発生した反応種と接触しない、請求項1に記載の蒸着方法。
- 前記反応空間がシャワーヘッド反応器の部分であり、シャワーヘッドおよびサセプタを含む、請求項1に記載の蒸着方法。
- 前記シャワーヘッドおよびサセプタの間に約0.5cm〜約5cmの隙間がある、請求項17に記載の方法。
- (a)少なくとも1つの三次元の形を有する基板を反応空間に充填する工程、
(b)ケイ素前駆体が、前記基板の表面に吸着されるように前記ケイ素前駆体を前記反応空間に導入する工程、
(c)過剰のケイ素含有前駆体および反応副生成物の前記反応空間をパージする工程、
(d)窒素前駆体を前記反応空間に導入する工程、
(e)前記反応空間の過剰の窒素前駆体および反応副生成物をパージする工程、
を含む窒化ケイ素薄膜の蒸着方法であって、
所望の厚さの窒化ケイ素薄膜が形成されるまで段階(b)〜(e)を繰り返し、
前記ケイ素含有前駆体が、ヨウ素または臭素を含み、
前記窒化ケイ素薄膜が、少なくとも1つの三次元機構に約50%超のステップカバレッジを有し、
前記窒化ケイ素薄膜のエッチング速度が0.5%のHF水溶液中約5nm/分未満であり、
前記少なくとも1つの三次元機構の上面における前記窒化ケイ素薄膜のエッチング速度に対する前記少なくとも1つの三次元機構の側壁における前記窒化ケイ素薄膜のエッチング速度の割合が約4未満である、窒化ケイ素薄膜の蒸着方法。 - 前記窒化ケイ素薄膜が、約80%超のステップカバレッジを有する、請求項19に記載の蒸着方法。
- 前記窒化ケイ素薄膜が、約90%超のステップカバレッジを有する、請求項19に記載の蒸着方法。
- 前記プロセスが熱的原子層堆積プロセスである、請求項19に記載の蒸着方法。
- 前記プロセスがプラズマで増幅された熱的原子層堆積プロセスである、請求項19に記載の蒸着方法。
- 前記ケイ素含有前駆体が、一般式(9)〜(20)の1つの式を有する、請求項19に記載の蒸着方法。
- 前記ケイ素含有前駆体が、HSiI3、H2SiI2、H3SiI、H2Si2I4、H4Si2I2、H5Si2I、MeSiI3、Me2SiI2、Me3SiI、Me2Si2I4、Me4Si2I2、HMeSiI2、H2Me2Si2I2、EtSiI3、Et2SiI2、Et3SiI、Et2Si2I4、Et4Si2I2、およびHEtSiI2からなる群から選択される、請求項19に記載の蒸着方法。
- 前記ケイ素含有前駆体がH2SiI2である、請求項25に記載の蒸着方法。
- 前記方法が、約300℃〜約400℃の温度で行われる、請求項19に記載の蒸着方法。
- 前記窒化ケイ素薄膜が、ステップカバレッジおよび少なくとも約80%のパターン負荷効果を示す、請求項19に記載の蒸着方法。
- 前記少なくとも1つの三次元機構の上面/領域における前記窒化ケイ素薄膜のエッチング速度に対する前記少なくとも1つの三次元機構の側壁における前記窒化ケイ素薄膜のエッチング速度が約3未満である、請求項19に記載の蒸着方法。
- 前記少なくとも1つの三次元機構の上面/領域における前記窒化ケイ素薄膜のエッチング速度に対する前記少なくとも1つの三次元機構の側壁における前記窒化ケイ素薄膜のエッチング速度が、約1である、請求項19に記載の蒸着方法。
- 前記エッチング速度が、約3nm/分未満である、請求項19に記載の蒸着方法。
- (a)前記ケイ素前駆体が前記基板の表面に吸着されるように、前記基板を気相のケイ素前駆体に曝す工程、
(b)前記基板をパージガスおよび/または真空に曝して、前記基板表面から過剰のケイ素前駆体および反応副生成物を除去する工程、
(c)前記吸着されたケイ素反応物質を窒素前駆体と接触させる工程、ならびに
(d)前記基板をパージガスおよび/または真空に曝して、前記基板表面および前記基板表面付近からの窒素を含有するプラズマおよび反応副生成物の種を除去する工程、
を含む基板上への窒化ケイ素薄膜の蒸着方法であって、
工程(a)〜(d)が所望の厚さの窒化ケイ素フィルムが形成されるまで繰り返され、
前記ケイ素反応物質がヨウ素または臭素を含む、窒化ケイ素薄膜の蒸着方法。 - (a)前記ケイ素反応物質が前記基板表面に吸着されるように、前記基板を気相ケイ素反応物質に曝す工程、
(b)前記基板をパージガスおよび/または真空に曝して、前記基板表面から過剰のケイ素反応物質および反応副生成物を除去する工程、
(c)前記吸着されたケイ素反応物質を窒素含有プラズマにより生成された種と接触させる工程、
(d)前記基板をパージガスおよび/または真空に曝して、前記基板表面および前記基板表面付近から前記過剰の窒素前駆体を除去する工程、
を含む、少なくとも1つの三次元機構を含む基板上への窒化ケイ素薄膜の蒸着方法であって、
所望の厚さの窒化ケイ素薄膜が形成されるまで段階(a)〜(d)を繰り返し、
ここで、前記ケイ素含有前駆体がヨウ素または臭素を含有し、
前記窒化ケイ素薄膜が、約50%超のステップカバレッジを有し、
前記窒化ケイ素薄膜のエッチング速度が0.5%のHF水溶液中約5nm/分未満であり、ならびに
前記少なくとも1つの三次元機構の上面における前記窒化ケイ素薄膜のエッチング速度に対する前記少なくとも1つの三次元機構の側壁における前記窒化ケイ素薄膜のエッチング速度の割合は約4未満である、窒化ケイ素薄膜の蒸着方法。 - 前記第二反応物質が窒素前駆体を含む、請求項34に記載の方法。
- 前記窒素前駆体が、窒素含有プラズマ由来の反応種を含む、請求項35に記載の方法。
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