JP7246990B2 - エッチング液、及びエッチング方法 - Google Patents
エッチング液、及びエッチング方法 Download PDFInfo
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- JP7246990B2 JP7246990B2 JP2019059172A JP2019059172A JP7246990B2 JP 7246990 B2 JP7246990 B2 JP 7246990B2 JP 2019059172 A JP2019059172 A JP 2019059172A JP 2019059172 A JP2019059172 A JP 2019059172A JP 7246990 B2 JP7246990 B2 JP 7246990B2
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- 238000005530 etching Methods 0.000 title claims description 169
- 238000000034 method Methods 0.000 title claims description 44
- 239000007788 liquid Substances 0.000 title claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 110
- 239000002608 ionic liquid Substances 0.000 claims description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 59
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 55
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 45
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 31
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- 125000005496 phosphonium group Chemical group 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 62
- 239000000654 additive Substances 0.000 description 49
- 230000000996 additive effect Effects 0.000 description 46
- 239000000243 solution Substances 0.000 description 37
- 150000003377 silicon compounds Chemical class 0.000 description 36
- 239000007864 aqueous solution Substances 0.000 description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 25
- 239000000428 dust Substances 0.000 description 24
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 230000008569 process Effects 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 23
- 239000010703 silicon Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 12
- 239000007853 buffer solution Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- -1 Fluorine ions Chemical class 0.000 description 5
- 150000004693 imidazolium salts Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910017008 AsF 6 Inorganic materials 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000000738 capillary electrophoresis-mass spectrometry Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical group C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Description
第1実施形態に係るエッチング液は、窒化シリコンのエッチングに用いられる。このエッチング液は、特に、酸化シリコンと窒化シリコンとを含む構造から、窒化シリコンのみを選択的に除去するためのエッチング液として好適に用いられる。
フッ化水素は、下記式(2)に示すように、窒化シリコン(Si3N4)のエッチャントとしてはたらき、窒化シリコンを、四フッ化ケイ素(SiF4)とアンモニア(NH3)とに分解する。
また、フッ化水素は、下記式(3)及び(4)に示すように電離する。
HF + F- → HF2 - (4)
フッ素イオン(F-)は、窒化シリコンのエッチャントとして特に強くはたらく。その一方、フッ化水素は、下記式(5)に示すように、酸化シリコン(SiO2)のエッチャントとしてもはたらき、酸化シリコンをケイフッ化水素酸(H2SiF6)及び水(H2O)に分解する。この反応は可逆反応である。
すなわち、フッ化水素は、窒化シリコンのエッチングレートを高める一方で、酸化シリコンのエッチングレートも高めるため、選択比を向上させにくい。
第2実施形態に係る添加剤は、シリコン又はシリコン含有物のエッチングに用いるエッチング液に添加される。添加剤は、イオン性液体を含む。
第3実施形態に係るエッチング液は、第2実施形態に係る添加剤と酸性水溶液とを含む。第3実施形態に係るエッチング液は、エッチング原液に第2実施形態に係る添加剤を添加することにより得られる。
第4実施形態に係るエッチング方法は、第1実施形態に係るエッチング液を用いて、窒化シリコンのエッチングを行うことを含む。
第5実施形態に係るエッチング方法は、第3実施形態に係るエッチング液を用いて、シリコン又はシリコン含有物のエッチングを行うことを含む。シリコン含有物は、例えば、酸化シリコン又は窒化シリコンである。
上述した式(B05)で表されるイオン性液体(C6H11BF4N2O)を用いて、表1に示す組成の実施例1~実施例4に係るエッチング液を調製した。
上述した式(B08)で表されるイオン性液体(C7H13BF4N2)を用いて、表2に示す組成の実施例5~実施例8に係るエッチング液を調製した。
上述した式(B02)で表されるイオン性液体(C8H15BF4N2)を用いて、表3に示す組成の実施例9~実施例12に係るエッチング液を調製した。
上述した式(B04)で表されるイオン性液体(C12H23BF4N2)を用いて、表4に示す組成の実施例13に係るエッチング液を調製した。
上述した式(D01)で表されるイオン性液体(C9H14BF4N)を用いて、表5に示す組成の実施例14及び15に係るエッチング液を調製した。
上述した式(D02)で表されるイオン性液体(C10H16BF4N)を用いて、表6に示す組成の実施例16及び17に係るエッチング液を調製した。
上述した式(B08)で表されるイオン性液体(C7H13BF4N2)又は硫酸を用いて、表7に示す組成の実施例18~23及び比較例1~7に係るエッチング液を調製した。
先ず、基材として、一辺を2.5cmとする正方形状の単結晶シリコン板を準備した。この基材上に、酸化シリコン膜及び窒化シリコン膜を、基材の主面に対して垂直な方向に交互に並列するように形成して、処理基板を得た。この処理基板における酸化シリコン膜の厚さ及び窒化シリコン膜の厚さを、分光エリプソメータ(J.A.Woollam社製 M-2000)で測定した。測定は9か所で行い、処理前の酸化シリコン膜の厚さの平均値及び窒化シリコン膜の厚さの平均値を得た。
エッチング処理後のエッチング液中に析出した白色状の物質の量を、目視で確認した。この際、析出量が少ない又は無かったものを析出度1とし、やや析出したものを析出度2として、析出量が多かったものを析出度3とした。この結果を、表1乃至表7に示す。
以下、本願の出願当初の特許請求の範囲に記載した発明を付記する。
[1] 窒化シリコンのエッチングに用いるエッチング液であって、リン酸と、テトラフルオロホウ酸と、シリコン化合物と、水と、硫酸及びイオン性液体の少なくとも一方とを含むエッチング液。
[2] 前記テトラフルオロホウ酸の濃度は0.10質量%以上0.25質量%以下である[1]に記載のエッチング液。
[3] 前記エッチング液のシリカ濃度は1100ppm以上2500ppm以下である[1]又は[2]に記載のエッチング液。
[4] 前記水の濃度は7質量%以上10質量%以下である[1]乃至[3]の何れか1項に記載のエッチング液。
[5] 前記エッチング液は前記硫酸を含み、前記硫酸の濃度は13質量%以上25質量%以下である[1]乃至[4]の何れか1項に記載のエッチング液。
[6] 前記イオン性液体のアニオンは、BF 4 - 、及び、PF 6 - からなる群より選ばれる少なくとも1種である[1]乃至[5]の何れか1項に記載のエッチング液。
[7] 前記イオン性液体のカチオンは、イミダゾリウム骨格、ピリジニウム骨格、第4級アンモニウム骨格、第4級ホスホニウム骨格、ピロリジニウム骨格、モルホニウム骨格、ピペリジニウム骨格、及びスルホニウム骨格からなる群より選ばれる少なくとも1種を有する[1]乃至[6]の何れか1項に記載のエッチング液。
[8] [1]乃至[7]の何れか1項に記載のエッチング液を用いて、窒化シリコンのエッチングを行うことを含むエッチング方法。
[9] シリコン又はシリコン含有物のエッチング液に含まれる添加剤であって、イオン性液体を含む添加剤。
[10] 前記イオン性液体のアニオンは、BF 4 - 、及び、PF 6 - からなる群より選ばれる少なくとも1種である[9]に記載の添加剤。
[11] 前記イオン性液体のカチオンは、イミダゾリウム骨格、ピリジニウム骨格、第4級アンモニウム骨格、第4級ホスホニウム骨格、ピロリジニウム骨格、モルホニウム骨格、ピペリジニウム骨格、及びスルホニウム骨格からなる群より選ばれる少なくとも1種を有する[9]又は[10]に記載の添加剤。
[12] シリコン化合物を更に含む[9]乃至[11]の何れか1項に記載の添加剤。
[13] [9]乃至[12]の何れか1項に記載の添加剤と酸性水溶液とを含むエッチング液。
[14] 前記酸性水溶液は、硝酸、硫酸及びリン酸からなる群より選ばれる少なくとも1種の酸を含む[13]に記載のエッチング液。
[15] [13]又は[14]に記載のエッチング液を用いて、シリコン又はシリコン含有物のエッチングを行うことを含むエッチング方法。
Claims (7)
- 窒化シリコンのエッチングに用いるエッチング液であって、
リン酸と、水と、イオン性液体と、コロイダルシリカとを含み、
前記イオン性液体のアニオンは、BF4 -、及び、PF6 -からなる群より選ばれ、前記イオン性液体のカチオンは、イミダゾリウム骨格、ピリジニウム骨格、第4級アンモニウム骨格、第4級ホスホニウム骨格、ピロリジニウム骨格、モルホニウム骨格、ピペリジニウム骨格、及びスルホニウム骨格からなる群より選ばれ、
前記イオン性液体の濃度は、0.10質量%以上0.35質量%以下である、
エッチング液。 - 前記コロイダルシリカの濃度は880ppm以上2500ppm以下である、請求項1に記載のエッチング液。
- 前記水の濃度は7質量%以上10質量%以下である、請求項1に記載のエッチング液。
- 前記リン酸の濃度は89質量%以上93質量%以下である、請求項1に記載のエッチング液。
- さらに、テトラフルオロホウ酸を含む、請求項1乃至4の何れか1項に記載のエッチング液。
- 前記テトラフルオロホウ酸の濃度は0.01質量%以上0.06質量%以下である、請求項5に記載のエッチング液。
- 請求項1乃至6の何れか1項に記載のエッチング液を用いて、酸化シリコンと窒化シリコンとを含む構造から窒化シリコンを選択的に除去することを含むエッチング方法。
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