JP2017160488A - マスク構造体の形成方法及び成膜装置 - Google Patents
マスク構造体の形成方法及び成膜装置 Download PDFInfo
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- JP2017160488A JP2017160488A JP2016045989A JP2016045989A JP2017160488A JP 2017160488 A JP2017160488 A JP 2017160488A JP 2016045989 A JP2016045989 A JP 2016045989A JP 2016045989 A JP2016045989 A JP 2016045989A JP 2017160488 A JP2017160488 A JP 2017160488A
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- film
- forming
- tungsten
- gas
- silicon
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- 238000000034 method Methods 0.000 title claims abstract description 51
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- 239000007789 gas Substances 0.000 claims abstract description 120
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 238000012545 processing Methods 0.000 claims abstract description 27
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010937 tungsten Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims description 16
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- 230000007246 mechanism Effects 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000009413 insulation Methods 0.000 abstract 5
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- 238000012360 testing method Methods 0.000 description 76
- 238000011156 evaluation Methods 0.000 description 60
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- 229910021417 amorphous silicon Inorganic materials 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000002344 surface layer Substances 0.000 description 13
- 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 12
- 229910052581 Si3N4 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 5
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IVSPVXKJEGPQJP-UHFFFAOYSA-N 2-silylethylsilane Chemical compound [SiH3]CC[SiH3] IVSPVXKJEGPQJP-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- ZVJOQYFQSQJDDX-UHFFFAOYSA-N 1,1,2,3,3,4,4,4-octafluorobut-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)F ZVJOQYFQSQJDDX-UHFFFAOYSA-N 0.000 description 1
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
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- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- 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
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/311—Etching the insulating layers by chemical or physical means
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Abstract
Description
基板に形成された前記絶縁膜上に第1の処理ガスを供給して、シリコンと炭素と窒素と水素とを各々主成分として含む中間膜を形成する工程と、
次いで、タングステンの化合物を含む第2の処理ガスを前記基板に供給して、前記中間膜を構成するシリコンの一部をタングステンに置き換えてタングステン膜を形成する工程と、
を含むことを特徴とするマスク構造体の形成方法。
前記真空容器内の前記基板を加熱するための加熱機構と、
シリコンと炭素と窒素と水素とを各々主成分として含む中間膜を前記基板に形成するために第1の処理ガスを前記真空容器内に供給する第1のガス供給部と、
タングステンの化合物を含む第2の処理ガスを前記真空容器内に供給する第2のガス供給部と、
前記真空容器内の圧力を調整する圧力調整部と、
前記基板に形成された絶縁膜上に前記第1の処理ガスを供給して前記中間膜を形成する第1のステップと、次いで、タングステンの化合物を含む処理ガスを供給して、前記中間膜を構成するシリコンの一部をタングステンに置き換えてタングステン膜を形成する第2のステップと、が行われるように前記加熱機構、前記各ガス供給部及び前記圧力調整部を制御する制御部と、
を備えることを特徴とする成膜装置。
本発明に係る第1の実施の形態について、図面に基づき説明する。図1は成膜装置1の略縦断面図であり、図中2は例えば石英により縦型の円筒状に形成された反応容器である。この反応容器2の下端は炉口として開口され、その開口部21の周縁部にはフランジ22が一体形成されている。反応容器2の下方には、前記フランジ22の下面に当接して開口部21を気密に閉塞する例えば石英製の蓋体23が、図示しないボートエレベータにより上下方向に開閉可能に設けられている。蓋体23の中央部には、回転軸24が貫通して設けられ、その上端部には、基板保持具であるウエハボート3が搭載されている。
3Si+2WF6→2W+3SiF4・・・反応式1
第2の実施形態のマスク構造体の形成手法について、第1の実施形態との差異点を中心に説明する。上記のように工程S1を行い、中間膜82を形成した後、工程S2を行わず、工程S3を行い、WF6ガスを供給する(図10)。中間膜82を構成するSiの一部がWに置換され、W膜87が形成される(図11)。つまり、このW膜87は、上記の密着層85に相当し、W、Si、C,N、Hを主成分として含む膜である。なお、図では第1の実施形態のW膜と区別するためW膜87を、WSiCNとして表記している。
本発明に関連する評価試験について説明する。
(評価試験1)
評価試験1として、上記の工程S1と同様にウエハ10にジイソプロピルアミノシランガスを供給してCVDを行い、中間膜82を成膜した。然る後、この中間膜82についてラザフォード後方散乱分析法(RBS)により膜の組成を調べた。また、比較試験1として550℃に加熱したウエハ10にDCSガスとNH3ガスとを交互に繰り返し供給してALDを行い、SiN膜を成膜した。このSiN膜について評価試験1と同様にRBSにより膜の組成を調べた。下記の表1は、評価試験1及び比較試験1の結果を示すものであり、表中の数字の単位はatomic%である。
評価試験2−1として、既述の工程S1によって膜厚が7nmとなるように中間膜82を形成した。この評価試験2−1では、工程S2、S3については行わなかった。また、評価試験2−2として、第1の実施形態で説明したように工程S1〜S3を行い、中間膜82及びW膜84を形成した。さらに評価試験2−3として、第2の実施形態の図13、図14で説明したように、工程S1、S3、S2、S3をこの順に行い、中間膜82から形成されるW膜84とa−Si膜83から形成されるW膜87との積層膜を形成した。評価試験2−1〜2−3において、工程S1は図2に示したSiO2膜81が形成されたウエハ10に対して行った。そして、これら評価試験2−1〜2−3のウエハ10に対してSiMS(二次イオン質量分析法)を行った。
評価試験3として、処理毎に反応容器2内の温度を変えて上記の工程S1を行い、形成された中間膜82の膜厚を測定し、成膜レートを測定した。ガスは実施の形態と同様、ジイソプロピルアミノシランを用いた。図18のグラフは、この評価試験3の結果を示したものであり、グラフの縦軸は上記の成膜レート(単位:Å/分)、横軸は温度を(1000/温度(単位:K))として示している。グラフ中には試験結果をプロットで表示し、例えば温度が520℃であるときの成膜レートは1.4Å/分であった。さらに、各プロットから得られる近似直線をグラフに表示している。この近似直線より、実施の形態で説明したように温度が高いほど高い成膜レートを示した。
評価試験4として、第1の実施形態に従ってウエハ10にW膜84を成膜した。図8、図9で説明したように工程S2、S3を繰り返し行い、W膜84は10層積層された構成とした。1層あたりのW膜84の膜厚は225Åである。図19は、この評価試験4のウエハ10の模式図である。また、比較試験4として、SiO2膜81上に膜厚が500Åとなるようにa−Si膜83を形成し、然る後5分間O2ガスを供給して、a−Si膜83の表面に酸化層91を形成した。その後、評価試験4と同様に工程S2、S3を繰り返し行い、酸化層91上に互いに積層された10層のW膜84を形成した。1層あたりのW膜84の膜厚は評価試験4と同じ225Åである。図20は、この比較試験4のウエハ10の模式図である。
10 ウエハ
2 反応容器
20 制御部
3 ウエハボート
43、53、63、73 ガス供給源
81 SiO2膜
82 中間膜
83 アモルファスシリコン膜
84 W膜
Claims (7)
- シリコンと酸素とを含む絶縁膜の上にエッチング用のマスク構造体を形成する方法において、
基板に形成された前記絶縁膜上に第1の処理ガスを供給して、シリコンと炭素と窒素と水素とを各々主成分として含む中間膜を形成する工程と、
次いで、タングステンの化合物を含む第2の処理ガスを前記基板に供給して、前記中間膜を構成するシリコンの一部をタングステンに置き換えてタングステン膜を形成する工程と、
を含むことを特徴とするマスク構造体の形成方法。 - 前記中間膜を形成する工程を行った後、前記タングステン膜を形成する工程を行う前に行われる、前記中間膜上に第3の処理ガスを供給してシリコン膜を形成する工程を含み、
前記タングステン膜を形成する工程は、
前記シリコン膜に前記第2の処理ガスを供給し、当該シリコン膜を構成するシリコンをタングステンに置き換えてタングステン膜を形成する工程を含むことを特徴とする請求項1記載のマスク構造体の形成方法。 - 前記中間膜には炭素が10atomic%以上含まれることを特徴とする請求項1または2記載のマスク構造体の形成方法。
- 前記中間膜において、窒素の含有量よりもシリコンの含有量の方が多いことを特徴とする請求項1ないし3のいずれか1つに記載のマスク構造体の形成方法。
- 前記第1の処理ガスの供給を前記基板に開始してから前記タングステン膜を形成するまでの間、前記基板の周囲の雰囲気を真空雰囲気に維持する工程と、を備えることを特徴とする請求項1ないし5のいずれか1つに記載のマスク構造体の形成方法。
- 真空容器内に載置された基板に成膜処理を行う成膜装置において、
前記真空容器内の前記基板を加熱するための加熱機構と、
シリコンと炭素と窒素と水素とを各々主成分として含む中間膜を前記基板に形成するために第1の処理ガスを前記真空容器内に供給する第1のガス供給部と、
タングステンの化合物を含む第2の処理ガスを前記真空容器内に供給する第2のガス供給部と、
前記真空容器内の圧力を調整する圧力調整部と、
前記基板に形成された絶縁膜上に前記第1の処理ガスを供給して前記中間膜を形成する第1のステップと、次いで、タングステンの化合物を含む処理ガスを供給して、前記中間膜を構成するシリコンの一部をタングステンに置き換えてタングステン膜を形成する第2のステップと、が行われるように前記加熱機構、前記各ガス供給部及び前記圧力調整部を制御する制御部と、
を備えることを特徴とする成膜装置。
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