JP4674061B2 - 薄膜形成方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims description 102
- 239000010409 thin film Substances 0.000 title claims description 38
- 230000015572 biosynthetic process Effects 0.000 title claims description 33
- 239000007789 gas Substances 0.000 claims description 355
- 239000010408 film Substances 0.000 claims description 182
- 239000003054 catalyst Substances 0.000 claims description 61
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052721 tungsten Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 239000010937 tungsten Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 150000002429 hydrazines Chemical class 0.000 claims description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 13
- 150000004756 silanes Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- -1 tungsten halide Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003658 tungsten compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 235000003642 hunger Nutrition 0.000 claims description 2
- 230000037351 starvation Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 238000000231 atomic layer deposition Methods 0.000 description 45
- 230000004888 barrier function Effects 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 239000002243 precursor Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
実施例1において用いた反応性ガスであるNH3ガス及びSiH4ガスの流す順序を変え、最初にNH3ガスを流し、次いでSiH4ガスを流して同様にしてWxN成膜プロセスを実施した。得られたWxN膜中のwの比率は5以下であり、膜全体に占めるwの比率が1.5程度であるWxNが酸化物膜表面上に10%程度存在し、得られた膜の比抵抗は数千から数万μΩcmと高く、また、下地膜との密着性を劣化させた。
103 触媒室 104 シャッターバルブ
105 原料ガス導入配管 106 ガス噴出手段
107 ウェハー 108 触媒体
Claims (10)
- 真空チャンバー内に原料ガスとして、ハロゲン化タングステンガス、オキシハロゲン化タングステンガス、カルボニル化タングステンガス、又は有機タングステン化合物ガスを導入し、成膜対象物上に供給して吸着せしめた後、該原料ガスの供給を停止し、該真空チャンバー内を排気する工程と、化学構造中に水素原子及びケイ素原子を含んだ反応性ガス並びに水素原子及び窒素原子を含んだ反応性ガスを触媒体に接触させて活性種にしてから該真空チャンバー内に導入し、吸着している原料ガスと反応させた後、該反応性ガスの供給を停止し、該真空チャンバー内を排気する工程とを交互に繰り返して、該成膜対象物上にW系金属薄膜を形成することを特徴とする薄膜形成方法。
- 前記ハロゲン化タングステンガスがWF6又はWCl6ガスであり、オキシハロゲン化タングステンガスがWOF2、WOF4、WOCl2、又はWOCl4ガスであり、カルボニル化タングステンガスがW(CO)6又はW(CO)5ガスであり、有機タングステン化合物ガスがW(OC2H5)ガスであることを特徴とする請求項1記載の薄膜形成方法。
- 前記水素原子及びケイ素原子を含んだガスがシランガス、ジハロゲン化シランガスであり、水素原子及び窒素原子を含んだガスがNH3ガス、ヒドラジンガス、又はヒドラジン誘導体ガスであることを特徴とする請求項1又は2記載の薄膜形成方法。
- 前記シランガスがSiH4又はSi2H6ガスであり、ジハロゲン化シランガスがSiH2Cl2ガスであり、ヒドラジン誘導体ガスがヒドラジン中のHをCxHyで置換したものであることを特徴とする請求項3記載の薄膜形成方法。
- 真空チャンバー内に原料ガスとしてWF6又はW(CO)6ガスを導入し、成膜対象物上に供給して吸着せしめた後、該原料ガスの供給を停止し、該真空チャンバー内を排気する工程と、化学構造中に水素原子及びケイ素原子を含んだ反応性ガスを触媒体に接触させて活性種にしてから該真空チャンバー内に導入し、吸着している原料ガスと反応させた後、該反応性ガスの供給を停止し、該真空チャンバー内を排気する工程とを交互に繰り返して、成膜対象物上に薄膜を形成し、次いで真空チャンバー内に該原料ガスを導入し、成膜対象物上に形成された薄膜上に供給して吸着せしめた後、該原料ガスの供給を停止し、該真空チャンバー内を排気する工程と、化学構造中に水素原子及びケイ素原子を含んだ反応性ガス並びに水素原子及び窒素原子を含んだ反応性ガスを触媒体に接触させて活性種にしてから該真空チャンバー内に導入し、吸着している原料ガスと反応させた後、該反応性ガスの供給を停止し、該真空チャンバー内を排気する工程、又は化学構造中に水素原子のみを含んだ反応性ガス並びに水素原子及び窒素原子を含んだ反応性ガスを触媒体に接触させて活性種にしてから該真空チャンバー内に導入し、吸着している原料ガスと反応させた後、該反応性ガスの供給を停止し、該真空チャンバー内を排気する工程とを交互に繰り返して、該成膜対象物上にW又はWSixの薄膜と、WxN又はWxNySizの薄膜との積層膜を形成することを特徴とする薄膜形成方法。
- 前記水素原子及びケイ素原子を含んだ反応性ガスがシランガス、ジハロゲン化シランガスであり、前記水素原子及び窒素原子を含んだ反応性ガスがNH3ガス、ヒドラジンガス、ヒドラジン誘導体ガスであり、前記水素原子のみを含んだ反応性ガスが水素ガスであることを特徴とする請求項5記載の薄膜形成方法。
- 前記シランガスがSiH4ガス又はSi2H6ガスであり、前記ジハロゲン化シランガスがSiH2Cl2ガスであり、前記ヒドラジン誘導体ガスがヒドラジン中のHをCxHyで置換したものであることを特徴とする請求項6記載の薄膜形成方法。
- 真空チャンバー内に原料ガスとしてWF6又はW(CO)6ガスを導入して成膜対象物上に吸着せしめた後、該原料ガスの供給を停止し、該真空チャンバー内を排気する工程と、反応性ガスとして化学構造中に水素原子及びケイ素原子を含んだガスを触媒体に接触させて活性種にしてから真空チャンバー内に導入して成膜対象物上に吸着された原料ガスと反応せしめた後、該反応性ガスの供給を停止し、該真空チャンバー内を排気する工程とを交互に繰り返し、次いで該原料ガスを真空チャンバー内に導入して成膜対象物上に吸着せしめた後、該原料ガスの供給を停止し、該真空チャンバー内を排気する工程と、反応性ガスとして化学構造中に水素原子及び窒素原子を含んだガスを触媒体に接触させて活性種にしてから真空チャンバー内へ導入して成膜対象物上で吸着された原料ガスと反応させた後、該反応性ガスの供給を停止し、該真空チャンバー内を排気する工程とを交互に繰り返して、該成膜対象物上にWxN膜を形成することを特徴とする薄膜形成方法。
- 前記水素原子及びケイ素原子を含んだ反応性ガスがシランガス、ジハロゲン化シランガスであり、水素原子及び窒素原子を含んだ反応性ガスがNH3ガス、ヒドラジンガス、ヒドラジン誘導体ガスであることを特徴とする請求項8記載の薄膜形成方法。
- 前記シランガスがSiH4ガス又はSi2H6ガスであり、前記ジハロゲン化シランガスがSiH2Cl2ガスであり、前記ヒドラジン誘導体ガスがヒドラジン中のHをCxHyで置換したものであることを特徴とする請求項9記載の薄膜形成方法。
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