JP6929173B2 - シリコン酸化膜を形成する方法および装置 - Google Patents
シリコン酸化膜を形成する方法および装置 Download PDFInfo
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- JP6929173B2 JP6929173B2 JP2017175425A JP2017175425A JP6929173B2 JP 6929173 B2 JP6929173 B2 JP 6929173B2 JP 2017175425 A JP2017175425 A JP 2017175425A JP 2017175425 A JP2017175425 A JP 2017175425A JP 6929173 B2 JP6929173 B2 JP 6929173B2
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- film
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- oxide film
- silicon oxide
- silicon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 81
- 229910052814 silicon oxide Inorganic materials 0.000 title claims description 72
- 238000000034 method Methods 0.000 title claims description 60
- 239000007789 gas Substances 0.000 claims description 153
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 38
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 38
- 125000006850 spacer group Chemical group 0.000 claims description 34
- 230000000903 blocking effect Effects 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005121 nitriding Methods 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 294
- 229910004298 SiO 2 Inorganic materials 0.000 description 79
- 235000012431 wafers Nutrition 0.000 description 44
- 239000006185 dispersion Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000010926 purge Methods 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- -1 silane compound Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/401—Multistep manufacturing processes
- H01L29/4011—Multistep manufacturing processes for data storage electrodes
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Description
まず、本発明の一実施形態に係るシリコン酸化膜を形成する方法の適用例について説明する。図1は、本発明の一実施形態に係るシリコン酸化膜を形成する方法が適用される3D−NAND型不揮発性半導体装置の製造工程を示す工程断面図である。
次に、上記3D−NAND型不揮発性半導体装置の製造工程において実施される、本発明の一実施形態に係るシリコン酸化膜(ブロッキングオキサイド膜)を形成する方法について説明する。ブロッキングオキサイド膜は、犠牲膜であるSiN膜14をウエットエッチングにより除去する際に、SiN膜からなる電荷蓄積22がエッチングされることを防止するためのものである。
Si3N4+6H2O→3SiO2+N2O+4NH3 ・・・(1)
すなわち、熱エネルギーとO*およびH*を利用して、Si−Nの結合をSi−Oで置換する。具体的には、好ましくは、処理容器内の圧力を0.5〜10Torr(66.7〜1333Pa)にし、ウエハWを800〜900℃という高温に加熱して熱エネルギーを与えつつ、O2ガスおよびH2ガスを供給することにより、低圧ラジカル酸化(LPRO)の原理でO*およびH*を生成させ、図4(b)に示すように、スペーサSiN膜43に供給することにより、熱エネルギーとラジカルによってスペーサSiN膜43中で上記(1)式に従って、スペーサSiN膜43の一部がSiO2に置換されて置換SiO2膜44が形成されるとともに、N2OガスおよびNH3ガスを生成させ、最終的には、図4(c)のように、スペーサSiN膜43の全体が置換SiO2膜44となる(置換SiO2膜44の形成)。このとき、置換SiO2膜44は、スペーサSiN膜43よりも多少増膜する。例えば厚さ4nmのスペーサSiN膜43は、厚さ5nm程度の置換SiO2膜44となる。
次に、上記実施形態に係るシリコン酸化膜(ブロッキングオキサイド膜)を形成する方法を実施するための処理装置について説明する。
まず、ステップ4を上記第1の手法により行うことができる処理装置の第1の例について説明する。図7は処理装置の第1の例を示す縦断面図、図8はその水平断面図である。
次に、ステップ4を上記第2の手法により行うことができる処理装置の第2の例について説明する。図10は処理装置の第2の例を示す縦断面図、図11はその水平断面図である。
以上、本発明の実施の形態について説明したが、この発明は、上記の実施形態に限定されることはなく、その趣旨を逸脱しない範囲で種々変形可能である。
12;SiO2膜
14;SiN膜
21;ブロッキングオキサイド膜
43;スペーサSiN膜(犠牲膜)
44;置換SiO2膜
45;膜厚調整用SiO2膜
100,100′;処理装置
101;処理容器
101a;外管
101b;内管
102;本体部
120,120′;ガス供給機構
147,147a,147b;排気口
151;排気装置
152;加熱機構
160;制御部
W;半導体ウエハ(被処理体)
Claims (15)
- シリコン酸化膜とシリコン窒化膜が露出した被処理面にシリコン酸化膜を形成する方法であって、
シリコン酸化膜とシリコン窒化膜が露出した被処理面を有する被処理体を減圧下の処理容器内に配置された状態とする第1工程と、
前記シリコン酸化膜と前記シリコン窒化膜が露出した被処理面に犠牲膜となるスペーサシリコン窒化膜を成膜する第2工程と、
次いで、前記被処理体に熱エネルギーと酸素ラジカルおよび水素ラジカルを供給し、前記スペーサシリコン窒化膜をシリコン酸化膜に置換する第3工程と、
次いで、置換により形成された前記シリコン酸化膜の上に、膜厚調整用シリコン酸化膜を成膜する第4工程と
を有する、方法。 - 前記第3工程は、前記被処理体を800〜900℃の範囲の温度に加熱しつつ、酸素ガスおよび水素ガスを供給することにより、酸素ラジカルおよび水素ラジカルを生成し、前記酸素ラジカルおよび前記水素ラジカルにより、前記スペーサシリコン窒化膜を前記シリコン酸化膜に置換する、請求項1に記載の方法。
- 前記第2工程は、シリコン原料ガスと、窒化ガスとを交互に供給するALDにより前記シリコン窒化膜を成膜する、請求項1または請求項2に記載の方法。
- 前記第2工程は、前記シリコン原料ガスとして塩素含有シラン系ガスを用い、前記窒化ガスとしてアンモニアガスを用いて行われる、請求項3に記載の方法。
- 前記第4工程は、シリコン原料ガスと酸化種とを交互に供給するALDにより前記膜厚調整用シリコン酸化膜を成膜する、請求項1から請求項4のいずれか1項に記載の方法。
- 前記第4工程は、前記被処理体を700〜750℃に加熱しつつ、酸素ガスおよび水素ガスを供給することにより生成された酸素ラジカルおよび水素ラジカルを酸化種として用いる、請求項5に記載の方法。
- 前記第4工程は、酸化種としてオゾンガスを用いる、請求項5に記載の方法。
- 前記第4工程は、シリコン原料ガスとして、塩素含有シラン系ガスを用いる、請求項5から請求項7のいずれか1項に記載の方法。
- シリコン酸化膜とシリコン窒化膜が露出した被処理面は、前記被処理体としての3D−NAND型不揮発性半導体装置を形成する半導体ウエハにおいて、前記シリコン酸化膜と犠牲膜としての前記シリコン窒化膜の積層膜に積層方向に形成されたメモリホールに露出する前記積層膜の表面であり、前記被処理面に形成されるシリコン酸化膜は、ブロッキングオキサイド膜である、請求項1から請求項8のいずれか1項に記載の方法。
- シリコン酸化膜とシリコン窒化膜が露出した被処理面にシリコン酸化膜を形成する装置であって、
前記シリコン酸化膜とシリコン窒化膜が露出した被処理面を有する被処理体を収容する処理容器と、
前記処理容器内に所定のガスを供給するガス供給部と、
前記処理容器内を加熱する加熱機構と、
前記処理容器内を排気して減圧状態とする排気機構と、
前記ガス供給部、前記加熱機構、および前記排気機構を制御する制御部と
を具備し、
前記制御部は、
前記被処理体が前記処理容器内に配置された状態で、前記処理容器内を所定の減圧下に保持し、
前記シリコン酸化膜と前記シリコン窒化膜が露出した被処理面にシリコン原料ガスと窒化ガスとを用いて犠牲膜となるスペーサシリコン窒化膜を成膜し、
次いで、前記被処理体に熱エネルギーと酸素ラジカルおよび水素ラジカルを供給し、前記スペーサシリコン窒化膜をシリコン酸化膜に置換し、
次いで、置換により形成された前記シリコン酸化膜の上に、シリコン原料ガスと、酸化種とを交互に供給するALDにより膜厚調整用シリコン酸化膜を成膜するように、前記ガス供給部、前記加熱機構、および前記排気機構を制御する、装置。 - 前記制御部は、前記スペーサシリコン窒化膜をシリコン酸化膜に置換する際に、前記被処理体を800〜900℃の範囲の温度に加熱しつつ、酸素ガスおよび水素ガスを供給することにより、酸素ラジカルおよび水素ラジカルを生成し、前記酸素ラジカルおよび前記水素ラジカルにより、前記シリコン窒化膜が前記シリコン酸化膜に置換するように制御する、請求項10に記載の装置。
- 前記制御部は、前記スペーサシリコン窒化膜を成膜する際に、前記シリコン原料ガスとして塩素含有シラン系ガスを用い、前記窒化ガスとしてアンモニアガスを用いて、これらを交互に供給するALDにより成膜するように制御する、請求項10または請求項11に記載の装置。
- 前記制御部は、前記膜厚調整用シリコン酸化膜を成膜する際に、前記被処理体を700〜750℃に加熱しつつ、酸素ガスおよび水素ガスを供給することにより酸素ラジカルおよび水素ラジカルを生成させ、前記酸化種として用いるように制御する、請求項10から請求項12のいずれか1項に記載の装置。
- 前記ガス供給部は、前記膜厚調整用シリコン酸化膜を成膜する際に、前記酸化種としてオゾンガスを供給する、請求項10から請求項12のいずれか1項に記載の装置。
- コンピュータ上で動作し、シリコン酸化膜とシリコン窒化膜が露出した被処理面にシリコン酸化膜を形成する装置を制御するためのプログラムが記憶された記憶媒体であって、前記プログラムは、実行時に、請求項1から請求項9のいずれかの方法が行われるように、コンピュータに前記装置を制御させる、記憶媒体。
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