JP6989770B2 - ドライエッチング剤、ドライエッチング方法及び半導体装置の製造方法 - Google Patents
ドライエッチング剤、ドライエッチング方法及び半導体装置の製造方法 Download PDFInfo
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- 238000001312 dry etching Methods 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 42
- 239000004065 semiconductor Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000005530 etching Methods 0.000 claims description 79
- 239000007789 gas Substances 0.000 claims description 67
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000002210 silicon-based material Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- ULFHADFFJVZYKF-UHFFFAOYSA-N 2-fluoro-3-(trifluoromethyl)oxirane Chemical group FC1OC1C(F)(F)F ULFHADFFJVZYKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- FPFBPFZLHSYBAE-UHFFFAOYSA-N 2,2-difluoro-3-(trifluoromethyl)oxirane Chemical compound FC(F)(F)C1OC1(F)F FPFBPFZLHSYBAE-UHFFFAOYSA-N 0.000 claims description 3
- MYQUVHXMKCGPSC-UHFFFAOYSA-N 2,3-difluoro-2-(trifluoromethyl)oxirane Chemical compound FC1OC1(F)C(F)(F)F MYQUVHXMKCGPSC-UHFFFAOYSA-N 0.000 claims description 3
- DHGQMHOMRCABJL-UHFFFAOYSA-N 2-fluoro-2-(trifluoromethyl)oxirane Chemical compound FC(F)(F)C1(F)CO1 DHGQMHOMRCABJL-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229920006926 PFC Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 CF 3 CF = CFH Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 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 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 1
- TXOZSRCVHASUCW-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropan-1-ol Chemical compound OC(F)CC(F)(F)F TXOZSRCVHASUCW-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLNSPKBLFZKTHJ-UHFFFAOYSA-L [Si+2]=O.[F-].[F-] Chemical compound [Si+2]=O.[F-].[F-] YLNSPKBLFZKTHJ-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WBCLXFIDEDJGCC-UHFFFAOYSA-N hexafluoro-2-butyne Chemical compound FC(F)(F)C#CC(F)(F)F WBCLXFIDEDJGCC-UHFFFAOYSA-N 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical class FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Description
例えば、特許文献5には、フッ素化アルキル基を持つエポキシドの合成方法として、フルオロアルキル基を持つ置換オレフィンに対し、次亜フッ素酸(HOF)を用いて酸化反応を行うことで、対応するエポキシドを製造できることが開示されているので、この反応を用いて得ることができる。また、特許文献6には、パーフルオロプロペンに対する、次亜塩素酸ナトリウム(NaClO)を用いた酸化反応が開示されている。この反応を用いてハイドロフルオロアルキレンオキサイドを得ることができる。
ハイドロフルオロオレフィンの酸化以外の方法として、1,3,3,3-テトラフルオロアセト酢酸エチルを出発原料とし、多段階工程の反応を経て、1,3,3,3-テトラフルオロプロペンオキシドを得る方法が、非特許文献1に開示されている。この反応を用いてハイドロフルオロアルキレンオキサイドを得ることができる。
11 チャンバー
12 圧力計
13 高周波電源
14 下部電極
15 上部電極
16 ガス導入口
17 ガス排出ライン
18 試料
24 基板
25 エッチング対象層
26 レジスト膜
27 サイドエッチ
Claims (15)
- 少なくとも、化学式CF3-CxHyFzO(x=2または3、y=1,2,3,4または5、z=2x-1-y)で表され、酸素原子を含む三員環構造を有するハイドロフルオロアルキレンオキサイドを含むドライエッチング剤。
- さらに、不活性ガスを含む請求項1に記載のドライエッチング剤。
- さらに、添加ガス、及び不活性ガスを含む請求項1に記載のドライエッチング剤。
- 添加ガスが酸化性ガス、又は還元性ガスである、請求項3に記載のドライエッチング剤。
- 前記酸化性ガスが、含酸素ガス及び含ハロゲンガスからなる群から選ばれる少なくとも1種のガスであり、
前記含酸素ガスが、O2、O3、CO、CO2、COCl2、COF2、CF3OF、及びNO2からなる群から選ばれる少なくとも1種のガスであり、
前記含ハロゲンガスが、F2、NF3、Cl2、Br2、I2、CFCl3、CF2Cl2、CF3Cl、及びYFn(式中、YはCl、Br、又はIを表し、nは整数を表し、1≦n≦7である。)からなる群から選ばれる少なくとも1種のガスであり、
前記還元性ガスが、CH4、C2H2、C2H4、C2H6、C3H4、C3H6、C3H8、HF、HI、HBr、HCl、NO、NH3、及びH2からなる群より選ばれる少なくとも1種のガスである、請求項4に記載のドライエッチング剤。 - 前記不活性ガスがN2、He、Ar、Ne、及びKrからなる群より選ばれる少なくとも1種のガスである、請求項2~5のいずれか1項に記載のドライエッチング剤。
- 前記ハイドロフルオロアルキレンオキサイドの含有率が、1~60体積%である請求項1~6のいずれか1項に記載のドライエッチング剤。
- CF4、CF3H、CF2H2、CFH3、C2F6、C2F4H2、C2F5H、C3F8、C3F7H、C3F6H2、C3F5H3、C3F4H4、C3F3H5、C3F5H、C3F3H、C4F8、C4F6、C5F8、C5F10、C3F6、C3HF5、C3H2F4、C3H3F3、CF3I、CF2I2、及びCFI3からなる群より選ばれる少なくとも1種のガスをさらに含む、請求項1~7のいずれか1項に記載のドライエッチング剤。
- 前記ハイドロフルオロアルキレンオキサイドが、1,3,3,3-テトラフルオロプロピレンオキサイド、2,3,3,3-テトラフルオロプロピレンオキサイド、1,1,3,3,3-ペンタフルオロプロピレンオキサイド、及び、1,2,3,3,3-ペンタフルオロプロピレンオキサイドからなる群から選ばれる少なくとも1種である請求項1~8のいずれか1項に記載のドライエッチング剤。
- 前記ハイドロフルオロアルキレンオキサイドが1,3,3,3-テトラフルオロプロピレンオキサイドである請求項9に記載のドライエッチング剤。
- 少なくとも、化学式CF3-CxHyFzO(x=2または3、y=1,2,3,4または5、z=2x-1-y)で表され、酸素原子を含む三員環構造を有するハイドロフルオロアルキレンオキサイドを含むドライエッチング剤をプラズマ化して得られるプラズマガスを用いて、
二酸化シリコン、窒化シリコン、多結晶シリコン、アモルファスシリコン、及び炭化シリコンからなる群より選ばれる少なくとも1種のシリコン系材料を選択的にエッチングするドライエッチング方法。 - 前記ドライエッチング剤は、(A)前記ハイドロフルオロアルキレンオキサイドと、(B)H2、O2、CO、及びCOF2からなる群より選ばれる少なくとも1種以上のガスと、Arのみからなり、
(A)、(B)、及びArの体積流量比をそれぞれ1~60%:1~60%:5~98%(但し、各々のガスの体積流量比の合計は100%である。)であり、
前記シリコン系材料は、二酸化シリコン及び窒化シリコンからなる群より選ばれる少なくとも1種である請求項11に記載のドライエッチング方法。 - 前記ハイドロフルオロアルキレンオキサイドが1,3,3,3-テトラフルオロプロピレンオキサイドである請求項11又は12に記載のドライエッチング方法。
- さらに、水素と不活性ガスを含むドライエッチング剤を用いて、二酸化シリコンを選択的にエッチングする請求項11に記載のドライエッチング方法。
- 基板上に、二酸化シリコン、窒化シリコン、多結晶シリコン、アモルファスシリコン、及び炭化シリコンからなる群より選ばれる少なくとも1種のシリコン系材料膜を形成する工程と、
前記シリコン系材料膜の上に、所定の開口部を有するレジスト膜を形成する工程と、
請求項11に記載のドライエッチング方法を用いて、前記開口部から前記シリコン系材料膜をエッチングする工程と、
を含むことを特徴とする半導体装置の製造方法。
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