KR20210129350A - Etchant composition with high selectivity for nitride film - Google Patents
Etchant composition with high selectivity for nitride film Download PDFInfo
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- KR20210129350A KR20210129350A KR1020200047188A KR20200047188A KR20210129350A KR 20210129350 A KR20210129350 A KR 20210129350A KR 1020200047188 A KR1020200047188 A KR 1020200047188A KR 20200047188 A KR20200047188 A KR 20200047188A KR 20210129350 A KR20210129350 A KR 20210129350A
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- etchant composition
- silane
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 150000004767 nitrides Chemical class 0.000 title abstract description 24
- 229910000077 silane Inorganic materials 0.000 claims abstract description 55
- -1 silane inorganic acid salt Chemical class 0.000 claims abstract description 49
- 239000000654 additive Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 61
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 4
- 150000003839 salts Chemical class 0.000 claims 4
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 27
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 239000004065 semiconductor Substances 0.000 abstract description 16
- 239000010408 film Substances 0.000 description 41
- 230000008569 process Effects 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- 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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
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- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Weting (AREA)
Abstract
Description
본 발명은 질화막에 대한 선택성이 우수한 식각액 조성물에 관한 것으로, 좀더 상세하게 설명하자면, 무기산 용매와, 실란무기산염, 그리고 첨가제를 포함하되, 상기 실란무기산염으로 신규한 화합물을 사용함으로써, 질화막에 대한 식각 선택성이 우수하고, 나아가 친환경적이면서 경제적으로 반도체 소자를 제조할 수 있는 식각액 조성물에 관한 것이다.The present invention relates to an etchant composition having excellent selectivity for a nitride film, and to be more detailed, it includes an inorganic acid solvent, a silane inorganic acid salt, and an additive, but by using a novel compound as the silane inorganic acid salt, the nitride film The present invention relates to an etchant composition having excellent etch selectivity and capable of manufacturing a semiconductor device in an environmentally friendly and economical manner.
일반적으로 반도체 제조 공정에서는 실리콘 산화막(SiO2) 또는 실리콘 질화막(SiNx)을 각각 단독 또는 교대로 적층하고, 식각액(etchant)을 이용한 식각공정을 거쳐서 웨이퍼에 회로패턴을 형성한다. 상기 식각공정은 교대로 적층되어 있는 산화막과 질화막 중 질화막만을 제거하는 공정으로서 습식법과 건식법이 있는데, 최근에는 인산(phosphoric acid)과 탈이온수(deionized water)를 포함하는 식각액을 사용한 습식법이 주로 사용되고 있다. In general, in a semiconductor manufacturing process, a silicon oxide film (SiO 2 ) or a silicon nitride film (SiN x ) is individually or alternately stacked, and a circuit pattern is formed on a wafer through an etching process using an etchant. The etching process is a process of removing only the nitride film among the oxide film and the nitride film which are alternately stacked, and there are a wet method and a dry method. Recently, a wet method using an etching solution containing phosphoric acid and deionized water is mainly used. .
습식 식각법에 사용되는 식각액 중 탈이온수는 식각율 감소 및 산화막에 대한 식각 선택성의 변화를 방지하기 위하여 첨가되는 것이나, 식각액 내에서의 미세한 양 변화에도 질화막 식각 공정에 불량을 발생시키는 문제가 있다. 또한, 인산은 강산으로서 강한 부식성을 가지고 있어 취급에 어려움이 있다.Among the etchants used in the wet etching method, deionized water is added to prevent a decrease in the etch rate and a change in etch selectivity for the oxide film, but there is a problem in that the nitride film etching process is defective even with a slight change in the amount of the etchant. In addition, phosphoric acid is a strong acid and has a strong corrosive property, so it is difficult to handle.
그래서 인산(H3PO4)에 불산(HF) 또는 질산(HNO3) 등을 포함하는 식각액 조성물이 제시 되었으나, 이러한 식각액 조성물은 질화막과 산화막에 대한 식각 선택성이 불량한 문제점이 있다. 또한, 인산과 규산염, 또는 규산을 포함하는 식각액 조성물을 이용하는 기술도 개발 되었으나, 규산이나 규산염은 부산물을 발생시켜서 반도체 소자의 특성에 악영향을 미치는 것으로 드러났다. So, an etchant composition containing phosphoric acid (H 3 PO 4 ), hydrofluoric acid (HF) or nitric acid (HNO 3 ), etc. has been proposed, but such an etchant composition has a problem in that the etching selectivity for the nitride film and the oxide film is poor. In addition, a technique using phosphoric acid, silicate, or an etchant composition containing silicic acid has been developed, but it has been found that silicic acid or silicate generates by-products and adversely affects the characteristics of semiconductor devices.
이러한 문제점을 해결하고자 최근 등록특허 제10-1539373호(2015년 07월 20일) 및 제10-2024758호(2019년 09월 18일) 등에서는 고가의 알코올이나 할라이드기가 포함되어 있는 실리카 전구체를 사용한 식각액 조성물을 사용하고 있다. 이러한 식각액 조성물은 질화막에 대한 식각 선택성이 우수한 장점이 있으나, 식각 과정에서 염산, 알코올 등의 부산물을 생성하기 때문에 고온에서 이들 부산물을 증발시켜 제거하는 공정을 거쳐야 한다. In order to solve this problem, recently registered Patent Nos. 10-1539373 (July 20, 2015) and No. 10-2024758 (September 18, 2019), etc. use silica precursors containing expensive alcohols or halide groups. An etchant composition is used. Such an etchant composition has the advantage of excellent etch selectivity with respect to the nitride film, but since by-products such as hydrochloric acid and alcohol are generated during the etching process, these by-products must be removed by evaporating them at a high temperature.
결국 상기 식각액 조성물은 반도체 생산 공정에서 에너지 소모가 증가하여 경제성이 저하되고, 또한 환경 유해성 물질을 발생시키는 문제점이 있다. 따라서 반도체 제조 공정에서는 여전히 산화막에 대하여 질화막을 선택적으로 식각하면서도 부산물 발생과 같은 문제점을 갖지 않는 친환경적인 식각액 조성물의 개발이 요구되고 있다.As a result, the etchant composition has a problem in that energy consumption increases in the semiconductor production process, thereby lowering economic efficiency and generating environmentally harmful substances. Therefore, in the semiconductor manufacturing process, the development of an eco-friendly etchant composition that does not have problems such as generation of by-products while selectively etching the nitride film with respect to the oxide film is required.
본 발명의 목적은, 반도체 제조공정에서 반도체 소자의 특성에 악영향을 미치거나, 환경오염의 원인이 될 수 있는 부산물을 발생시키지 않으면서, 질화막에 대하여 우수한 식각 선택성을 갖는 새로운 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide a novel etchant composition having excellent etch selectivity for a nitride film without adversely affecting the characteristics of a semiconductor device in a semiconductor manufacturing process or generating by-products that may cause environmental pollution .
본 발명의 다른 목적은, 무기산 용매와, 실란무기산염, 그리고 첨가제를 포함하되, 상기 실란무기산염으로서 종래에는 식각액 조성물에 사용된 적이 없는 신규한 실란무기산염 화합물을 사용한 새로운 조성의 식각액 조성물을 제공하는 것이다.Another object of the present invention is to provide an etchant composition of a novel composition including an inorganic acid solvent, a silane inorganic acid salt, and an additive, but using a novel silane inorganic acid salt compound that has not been used in an etchant composition before as the silane inorganic acid salt will do
본 발명에 따른 식각액 조성물은, 무기산 용매와, 하기 [화학식 1]로 표시되는 실란무기산염, 그리고 첨가제를 포함하여 이루어지는 것을 특징으로 한다.The etchant composition according to the present invention is characterized in that it comprises an inorganic acid solvent, a silane inorganic acid salt represented by the following [Formula 1], and an additive.
[화학식 1][Formula 1]
(상기 화학식 1에서, R1 내지 R5는 각각 수소, 할로겐, C1~C12의 알킬기, C1~12의 알콕시기 이고; M은 0을 포함하는 양의 정수이다.)(In Formula 1, R 1 to R 5 are each hydrogen, halogen, a C1 to C12 alkyl group, and a C1 to 12 alkoxy group; M is a positive integer including 0.)
상기 [화학식 1]로 표시되는 실란무기산염은, 폴리인산을 포함하는 농도 99% 이상의 고농도 인산과, 하기 [화학식 2], [화학식 3] 또는 [화학식 4]로 표시되는 실란화합물 중 어느 하나를 반응시켜서 제조된 것임을 특징으로 한다.The silane inorganic acid salt represented by the [Formula 1] is a high concentration phosphoric acid containing polyphosphoric acid of 99% or more, and any one of the silane compounds represented by the following [Formula 2], [Formula 3] or [Formula 4] It is characterized in that it is prepared by reacting.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
(상기 화학식 3에서, OH기는 합성 조건에 따라 O- 또는 OH2가 될 수 있으며; R31 내지 R34는 각각 수소 원자, 할로겐 원자, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기 중에서 선택된 어느 하나이고; j, k, m, n은 각각 0을 포함하는 양의 정수이다.)(In Formula 3, the OH group may be O − or OH 2 depending on synthesis conditions; R 31 to R 34 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. any one selected; j, k, m, and n are each a positive integer including 0.)
[화학식 4][Formula 4]
(상기 화학식 4에서, OH기는 합성 조건에 따라 O- 또는 OH2가 될 수 있으며; R41내지 R43은 각각 수소 원자, 할로겐 원자, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기 중에서 선택된 어느 하나이다.)(In Formula 4, the OH group may be O − or OH 2 depending on synthesis conditions; R 41 to R 43 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. whichever one is chosen.)
본 발명의 바람직한 실시예에 따른 식각액 조성물은, 농도가 83 내지 87%인 인산 수용액 93 내지 98 중량%와, 상기 [화학식 1]로 표시되는 실란무기산염 0.2 내지 3 중량%와, 염화암모늄 1 내지 7 중량%를 포함하여 구성되고, 상기 실란무기산염은, 인(P) 원자가 2 내지 5개인 폴리인산 100 중량부에다 이산화규소(SiO2) 2 내지 6 중량부를 반응시켜서 제조된 것임을 특징으로 한다.The etchant composition according to a preferred embodiment of the present invention contains 93 to 98% by weight of an aqueous solution of phosphoric acid having a concentration of 83 to 87%, 0.2 to 3% by weight of the silane inorganic acid salt represented by the above [Formula 1], and 1 to 1 to ammonium chloride It comprises 7 wt%, and the silane inorganic acid salt is prepared by reacting 2 to 6 parts by weight of silicon dioxide (SiO 2 ) with 100 parts by weight of polyphosphoric acid having 2 to 5 phosphorus (P) atoms.
본 발명에 따른 식각액 조성물은 상기 [화학식 1]의 실란무기산염이 신규한 화합물로서, 산화막의 표면에 보호막을 형성하여 상대적으로 질화막만을 선택적으로 식각하는 효능이 있다.The etchant composition according to the present invention is a novel compound of the silane inorganic acid salt of [Formula 1], and has an effect of selectively etching only the nitride film relatively by forming a protective film on the surface of the oxide film.
또한, 본 발명에 따른 식각액 조성물은 비교적 저렴한 비정형 실란화합물을 사용하면서도 종래의 식각액 조성물과 유사한 식각 선택성을 발휘함으로써, 반도체 소자를 보다 경제적으로 제조할 수 있는 효과가 있다.In addition, the etchant composition according to the present invention exhibits etch selectivity similar to that of the conventional etchant composition while using a relatively inexpensive amorphous silane compound, thereby making it possible to manufacture a semiconductor device more economically.
이하, 바람직한 실시예를 이용하여 본 발명을 상세하게 설명한다. 다만, 본 발명에 대한 실시예는 다양한 변형이 가능하므로, 이들 실시예에 의해서 본 발명의 권리범위가 제한되는 것은 아니다. 또한 본 발명을 실시하는데 꼭 필요한 구성이라 하더라도 종래기술에 소개되어 있거나, 통상의 기술자가 공지기술로부터 용이하게 실시할 수 있는 사항에 대해서는 구체적인 설명을 생략한다.Hereinafter, the present invention will be described in detail using preferred embodiments. However, since various modifications are possible in the embodiments of the present invention, the scope of the present invention is not limited by these embodiments. In addition, even if it is a configuration essential for carrying out the present invention, a detailed description of the matter introduced in the prior art or that can be easily implemented by a person skilled in the art from the known art will be omitted.
본 발명에 따른 식각액 조성물은 반도체 소자의 제조공정에서 질화막을 식각하는 용도로 사용되는 것으로, 무기산 용매와, 실란무기산염, 그리고 첨가제를 포함하여 구성된다. 상기 질화막은 실리콘 질화막, 예컨대 SiN막이나 SiON막 등을 포함할 수 있다.The etchant composition according to the present invention is used for etching a nitride film in a semiconductor device manufacturing process, and includes an inorganic acid solvent, a silane inorganic acid salt, and an additive. The nitride film may include a silicon nitride film, for example, a SiN film or an SiON film.
먼저 무기산 용매는, 황산, 질산, 인산, 규산, 불산, 붕산, 염산, 과염소산 중에서 선택된 어느 하나 이상을 사용할 수 있고, 이중에서 인산, 특히 농도 83~87%의 인산 수용액을 사용하는 것이 바람직하다. 상기 인산 수용액에 사용되는 물은 특별히 한정하는 것은 아니지만, 탈이온수인 것이 바람직하다.First, as the inorganic acid solvent, any one or more selected from sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, and perchloric acid may be used. Although the water used for the said phosphoric acid aqueous solution is not specifically limited, It is preferable that it is deionized water.
상기 무기산 용매는 질화막을 식각하는 기능을 하는 것으로, 조성물 전체 중량의 80 내지 99.9 중량%를 포함하는 것이 바람직하다. 상기 무기산 용매의 함량이 80 중량% 미만이면 실리콘 화합물의 농도가 높아져서 실리콘 산화막에 실리콘이 증착되는 현상이나 실리콘 화합물의 석출 등이 발생될 수 있는 문제점이 생길 수 있고, 반대로 99.9 중량%를 초과하면 상대적으로 실란무기산염의 함량이 낮아져서 실리콘 질화막에 대한 식각 선택성이 저하될 수 있다.The inorganic acid solvent serves to etch the nitride film, and preferably contains 80 to 99.9 wt% of the total weight of the composition. When the content of the inorganic acid solvent is less than 80% by weight, the concentration of the silicon compound is increased, so that there may be a problem in that silicon deposition on the silicon oxide film or precipitation of the silicon compound may occur. Therefore, the content of the silane inorganic acid salt may be lowered, and thus the etch selectivity for the silicon nitride layer may be reduced.
다음으로 상기 실란무기산염은, 다음 [화학식 1]로 표시되는 화합물을 사용한다. 참고로 다음 [화학식 1]의 실란무기산염은 종래 식각액 조성물에서 사용된 적이 없는 신규한 화합물이다.Next, the silane inorganic acid salt uses a compound represented by the following [Formula 1]. For reference, the silane inorganic acid salt of the following [Formula 1] is a novel compound that has not been used in a conventional etchant composition.
[화학식 1][Formula 1]
(상기 화학식 1에서, R1 내지 R5는 각각 수소, 할로겐, C1~C12의 알킬기, C1~12의 알콕시기이고; M은 0을 포함하는 양의 정수이다.)(In Formula 1, R 1 to R 5 are each hydrogen, halogen, a C1 to C12 alkyl group, and a C1 to 12 alkoxy group; M is a positive integer including 0.)
상기 실란무기산염은 산화막의 표면에 보호막을 형성하는 기능을 하는 것으로, 상기 실란무기산염에 포함된 산소들이 산화막의 표면에 수소결합을 함으로써, 상기 식각액 조성물에 의해 질화막이 식각되는 동안, 산화막의 식각을 최소화 한다. 상기 실란무기산염은 소량으로도 산화막을 효과적으로 보호할 수 있고, 따라서 소량으로도 질화막에 대한 식각 선택성을 증가시킬 수 있다.The silane inorganic acid salt functions to form a protective film on the surface of the oxide film, and oxygen contained in the silane inorganic acid salt bonds to the surface of the oxide film by hydrogen bonding, so that while the nitride film is etched by the etchant composition, the oxide film is etched to minimize The silane inorganic acid salt can effectively protect the oxide layer even in a small amount, and thus can increase the etch selectivity to the nitride layer even in a small amount.
상기 실란무기산염의 함량은 조성물 전체 중량에 대하여 0.01 내지 8 중량%를 포함할 수 있다. 상기 실란무기산염의 함량이 0.01 중량% 미만이면, 실리콘 질화막에 대하여 원하는 식각 선택성을 기대하기 어렵고, 반대로 8 중량%를 초과하는 경우에는 상기 실란무기산염에 포함되어 있는 실리카 성분이 오히려 산화막에 증착될 수 있으므로 바람직하지 않다. The content of the silane inorganic acid salt may include 0.01 to 8% by weight based on the total weight of the composition. If the content of the silane inorganic acid salt is less than 0.01 wt %, it is difficult to expect a desired etching selectivity for the silicon nitride film, and on the contrary, if it exceeds 8 wt %, the silica component contained in the silane inorganic acid salt is rather deposited on the oxide film. It is not preferable because it can
상기 [화학식 1]로 표시되는 실란무기산염은, 폴리인산을 포함하는 고농도 인산과, 하기 [화학식 2], [화학식 3] 또는 [화학식 4]로 표시되는 실란화합물을 반응시켜서 제조된 것을 사용할 수 있다. The silane inorganic acid salt represented by the [Formula 1] may be prepared by reacting a high concentration phosphoric acid containing polyphosphoric acid with a silane compound represented by the following [Formula 2], [Formula 3] or [Formula 4]. have.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
(상기 화학식 3에서, OH기는 합성 조건에 따라 O- 또는 OH2가 될 수 있으며; R31 내지 R34는 각각 수소 원자, 할로겐 원자, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기 중에서 선택된 어느 하나이고; j, k, m, n은 각각 0을 포함하는 양의 정수이다.)(In Formula 3, the OH group may be O − or OH 2 depending on synthesis conditions; R 31 to R 34 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. any one selected; j, k, m, and n are each a positive integer including 0.)
[화학식 4] [Formula 4]
(상기 화학식 4에서, OH기는 합성 조건에 따라 O- 또는 OH2가 될 수 있으며; R41내지 R43은 각각 수소 원자, 할로겐 원자, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기 중에서 선택된 어느 하나이다.)(In Formula 4, the OH group may be O − or OH 2 depending on synthesis conditions; R 41 to R 43 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. whichever one is chosen.)
본 발명에서 고농도 인산이라 함은 농도가 99% 이상인 인산을 의미한다. 인산 수용액에 포함되어 있는 인산은 폴리머화가 가능하기 때문에 인산의 농도가 100% 이상이 될 수도 있고, 이처럼 인산의 농도가 100% 이상이 되면 폴리인산이 된다. 그리고 상기 실란화합물로는 상기 [화학식 2], [화학식 3] 또는 [화학식 4] 화합물 중에서 상기 [화학식 2] 화합물, 즉 이산화규소(SiO2)를 사용하는 것이 가장 바람직하다.In the present invention, high concentration phosphoric acid means phosphoric acid having a concentration of 99% or more. Since the phosphoric acid contained in the phosphoric acid aqueous solution is polymerizable, the concentration of phosphoric acid may be 100% or more. And as the silane compound, it is most preferable to use the [Formula 2] compound, that is, silicon dioxide (SiO 2 ) among the compounds of [Formula 2], [Formula 3] or [Formula 4].
본 발명의 일 실시예에 따르면, 폴리인산을 포함하는 고농도 인산 100 중량부에 대하여 상기 [화학식 1] 내지 [화학식 3] 중 어느 하나의 실란화합물 0.1 내지 20 중량부를 첨가한 후, 공기 및 수분을 제거하면서 20 내지 300℃의 온도에서 반응시켜서 상기 [화학식 1]의 실란무기산염을 제조할 수 있다. 이때, 고농도 인산은 인산원자 2개를 포함하는 피로인산 일 수도 있고, 인산원자 3개 이상을 포함하는 폴리인산 일 수도 있다. 상기 폴리인산은 인산 원자가 2 내지 5인 것이 바람직하다. According to an embodiment of the present invention, after adding 0.1 to 20 parts by weight of the silane compound of any one of [Formula 1] to [Formula 3] with respect to 100 parts by weight of high concentration phosphoric acid including polyphosphoric acid, air and moisture The silane inorganic acid salt of [Formula 1] can be prepared by reacting at a temperature of 20 to 300 °C while removing. In this case, the high concentration phosphoric acid may be pyrophosphoric acid including two phosphoric acid atoms or polyphosphoric acid including three or more phosphoric acid atoms. The polyphosphoric acid preferably has 2 to 5 phosphoric acid atoms.
상기 실란무기산염의 제조공정에서, 상기 실란화합물의 사용량이 0.1 중량부 미만이면, 상기 실란무기산염이 원하는 식각 선택성을 발휘하지 못하는 문제가 있고, 20 중량부를 초과하는 경우에는 상기 실란화합물의 석출되거나, 비정형 구조가 생성될 수 있다. 또한 상기 반응온도가 20℃ 미만인 경우, 상기 실란화합물이 결정화 되거나 낮은 반응속도로 인해 상기 실란화합물이 기화될 우려가 있고, 반대로 300℃를 초과하는 경우 상기 폴리인산이 증발해 버리는 문제가 발생할 수 있다.In the manufacturing process of the silane inorganic acid salt, if the amount of the silane compound used is less than 0.1 parts by weight, there is a problem that the silane inorganic acid salt does not exhibit the desired etching selectivity, and when it exceeds 20 parts by weight, the silane compound is precipitated or , an atypical structure may be created. In addition, when the reaction temperature is less than 20 ℃, there is a risk that the silane compound is crystallized or the silane compound is vaporized due to a low reaction rate. .
상기 실란무기산염을 제조하는 과정에서 발생하는 휘발성 부산물은 감압 하에서 증류에 의하여 제거할 수 있다. 이러한 과정을 거쳐서 수득되는 상기 [화학식 1]의 실란무기산염은 정제과정을 거친 후에 식각액 조성물의 구성성분으로 사용할 수도 있고, 정제과정 없이 바로 사용할 수도 있다.Volatile by-products generated in the process of preparing the silane inorganic acid salt may be removed by distillation under reduced pressure. The silane inorganic acid salt of [Formula 1] obtained through this process may be used as a component of the etchant composition after a purification process, or may be used directly without a purification process.
마지막으로 상기 첨가제로는 암모늄염을 포함할 수 있다. 상기 암모늄염은 본 발명에 따른 식각액 조성물의 겔화를 방지하는 기능을 하는 것으로, 그 함량은 조성물 전체 중량의 0.01 내지 12 중량%인 것이 바람직하다. 상기 실란무기산염과 마찬가지로 상기 암모늄염 역시 소량으로도 어느 정도의 겔화 방지기능을 발휘할 수 있으나, 그 함량이 0.01 중량% 미만이면 원하는 효과를 기대하기 어렵고, 반대로 12 중량%를 초과하여 첨가하면 오히려 암모늄염이 겔화의 원인이 될 수 있다.Finally, the additive may include an ammonium salt. The ammonium salt functions to prevent gelation of the etchant composition according to the present invention, and the content thereof is preferably 0.01 to 12% by weight of the total weight of the composition. Like the silane inorganic acid salt, the ammonium salt can also exhibit a certain amount of gelation prevention function even in a small amount, but if the content is less than 0.01 wt%, it is difficult to expect a desired effect, and on the contrary, if it is added in excess of 12 wt%, the ammonium salt is rather It may cause gelation.
상기 암모늄염은 암모늄 이온을 갖는 화합물로서, 암모니아수, 암모늄 클로라이드, 암모늄 아세트산, 암모늄 인산염, 암모늄 과옥시이황산염, 암모늄 황산염, 암모늄 불산염 중 어느 하나 이상을 사용할 수 있다. The ammonium salt is a compound having an ammonium ion, and any one or more of aqueous ammonia, ammonium chloride, ammonium acetic acid, ammonium phosphate, ammonium peroxydisulfate, ammonium sulfate, and ammonium hydrofluoric acid may be used.
본 발명의 식각액 조성물은 상기 암모늄염 이외에도 통상적인 질화막 식각액 조성물에 사용되는 통상의 첨가제들을 더 포함할 수 있다. 이러한 첨가제로는 계면활성제, 금속이온 봉쇄제, 부식방지제 등을 들 수 있다.The etchant composition of the present invention may further include conventional additives used in a conventional etchant composition for a nitride film in addition to the ammonium salt. Examples of such additives include surfactants, sequestering agents, and corrosion inhibitors.
본 발명에 따른 식각액 조성물을 사용하여 반도체 소자를 제조하는데 필요한 식각공정을 수행하는 방법은 통상적인 반도체 제조공정에 사용되는 습식 식각방법, 예컨대 침지법이나 분사법 등에 의하여 이루어질 수 있다. A method of performing an etching process necessary for manufacturing a semiconductor device using the etchant composition according to the present invention may be performed by a wet etching method used in a typical semiconductor manufacturing process, for example, an immersion method or a spraying method.
또한, 이러한 식각공정은 50 내지 300℃의 온도, 바람직하게는 100 내지 200℃, 보다 바람직하게는 136℃ 내지 163℃의 온도에서 수행할 수 있고, 이러한 공정온도는 다른 공정과의 관계 등 여러 요인을 고려하여 필요에 따라 변경될 수 있다. In addition, this etching process may be performed at a temperature of 50 to 300 °C, preferably 100 to 200 °C, more preferably 136 °C to 163 °C, and this process temperature depends on several factors such as the relationship with other processes. It may be changed as necessary taking into account.
[실시예][Example]
1) 실란무기산염의 제조1) Preparation of silane inorganic acid salt
다음 [표 1]의 제조예와 같은 조건으로 폴리인산과 실란화합물을 반응시켜서 상기 [화학식 1]의 실란무기산염을 제조하였다. 상기 폴리인산은 인(P) 원자가 3개인 폴리인산을 사용하였다. 괄호 안의 숫자는 폴리인산과 실란화합물의 상대적인 사용량(중량부)이다.The silane inorganic acid salt of [Formula 1] was prepared by reacting polyphosphoric acid with a silane compound under the same conditions as in the preparation example of Table 1 below. As the polyphosphoric acid, polyphosphoric acid having three phosphorus (P) atoms was used. The number in parentheses is the relative amount (parts by weight) of polyphosphoric acid and silane compound.
2) 식각액 조성물의 제조2) Preparation of etchant composition
상기 [표 1]의 제조예 1 내지 6에 따라 제조된 실란무기산염을 이용하여 다음 [표 2]와 같은 조건으로 본 발명에 따른 식각액 조성물을 제조하였다. 구체적인 제조방법은 테프론 라이너 용기에 85% 인산 수용액과 상기 실란무기산염을 혼합 한 후 140℃로 승온하고, 2시간 교반하였다. 그리고 첨가제로서 염화암모늄을 투입하고 10분간 교반하였다.An etchant composition according to the present invention was prepared under the conditions shown in Table 2 below using the inorganic silane salts prepared according to Preparation Examples 1 to 6 of Table 1 above. In a specific manufacturing method, an 85% aqueous solution of phosphoric acid and the silane inorganic acid were mixed in a Teflon liner container, the temperature was raised to 140° C., and the mixture was stirred for 2 hours. Then, ammonium chloride was added as an additive and stirred for 10 minutes.
3) 식각성능 시험3) Etching performance test
상기 실시예 1 내지 6에 따라 제조된 본 발명의 식각액 조성물에 대하여 각각 식각성능을 시험하였다. 즉, 실리콘 산화막(SiO2)이 257.2㎛ 증착된 웨이퍼와, 실리콘 질화막(Si3N4)이 298.0㎛ 증착된 웨이퍼를 각각 준비하고, 이들 웨이퍼를 각각 상기 실시예 1 내지 6의 식각액 조성물에 충분히 잠기도록 담가준 다음, 오븐에서 160℃ 온도로 2시간 동안 식각공정을 진행하였다. Each of the etching performance of the etchant composition of the present invention prepared according to Examples 1 to 6 was tested. That is, a wafer on which a silicon oxide film (SiO 2 ) is deposited with 257.2 µm and a wafer on which a silicon nitride film (Si 3 N 4 ) is deposited with a silicon nitride film (Si 3 N 4 ) are prepared, respectively, and these wafers are sufficiently prepared in the etchant composition of Examples 1 to 6, respectively. After soaking, the etching process was performed in an oven at 160° C. for 2 hours.
상기 웨이퍼들을 증류수로 세척하고, 충분히 건조한 후 엘립소미터(NANO VIEW, SEMG-1000)를 이용하여 식각 이전과 식각 이후의 박막 두께(단위; ㎛)를 측정하고, 각각의 두께 차이를 바탕으로 식각 선택비를 산출한 다음, 그 결과를 다음 [표 3]에 수록하였다. 여기서 식각 선택비는 질화막의 두께 차이를 산화막의 두께 차이로 나눈 값이다.The wafers are washed with distilled water, dried sufficiently, and then the thin film thickness (unit: μm) before and after etching is measured using an ellipsometer (NANO VIEW, SEMG-1000), and the etching is based on the difference in thickness. After calculating the selection ratio, the results are listed in the following [Table 3]. Here, the etch selectivity is a value obtained by dividing the thickness difference of the nitride layer by the thickness difference of the oxide layer.
상기 [표 3]에서 선택비가 높다는 것은 질화막에 대한 식각 선택성이 높다는 것을 의미한다. 참고로 현재 반도체 제조공정에 사용되고 있는 식각액 조성물은 상기 선택비가 200 내지 1000, 바람직하기로는 300~700인 것을 사용하도록 권장하고 있다. 통상적으로 선택비가 높으면 높을수록 좋을 수 있다고 생각되나, 실제 산업계에서는 식각 공정의 소요시간이 비슷해야 균일한 품질의 반도체를 제조할 수 있으므로, 300~700의 범위 내에서 일정한 선택비를 갖는 조성물을 선호한다.A high selectivity in [Table 3] means that the etching selectivity for the nitride layer is high. For reference, it is recommended that the etchant composition currently used in the semiconductor manufacturing process be used with the selectivity ratio of 200 to 1000, preferably 300 to 700. In general, it is thought that the higher the selectivity is, the better it is, but in the actual industry, a composition having a constant selectivity within the range of 300 to 700 is preferred because the required time for the etching process is similar to manufacture a semiconductor of uniform quality. do.
이러한 관점에서 볼 때, 상기 실시예 1 내지 6에 따라 제조된 본 발명에 따른 질화막 식각액 조성물은 모두 반도체 소자의 제조공정에 사용하기에 적합한 것으로 확인되었다. 다만, 상기 실시예에는 나타내지 않았지만, 동일한 식각액 조성물을 사용하더라도 식각 공정의 온도를 높여 주면, 짧은 시간 내에 더 높은 선택비를 갖는 것으로 확인되었다.From this point of view, it was confirmed that all of the nitride film etchant compositions according to the present invention prepared according to Examples 1 to 6 were suitable for use in the manufacturing process of semiconductor devices. However, although not shown in the above examples, it was confirmed that even if the same etchant composition was used, when the temperature of the etching process was increased, a higher selectivity was obtained within a short time.
이와 같이 본 발명에 따른 식각액 조성물은 종래의 식각액에는 사용된 적이 없는 새로운 실란무기산염을 사용하는 것으로, 반도체 소자의 제조공정에 있어서 산화막에 대하여 질화막의 선택적 식각이 필요한 여러 과정에 효율적으로 적용될 수 있고, 나아가 종래의 식각액 조성물을 사용할 경우 문제가 되었던 부산물 생성을 방지하여 공정의 안정성 및 신뢰성을 확보할 수 있다.As described above, the etchant composition according to the present invention uses a new silane inorganic acid salt that has never been used in a conventional etchant, and can be efficiently applied to various processes requiring selective etching of a nitride film with respect to an oxide film in the manufacturing process of a semiconductor device. Furthermore, it is possible to secure the stability and reliability of the process by preventing the generation of by-products, which was a problem when using the conventional etchant composition.
Claims (8)
[화학식 1]
(상기 화학식 1에서, R1 내지 R5는 각각 수소, 할로겐, C1~C12의 알킬기, C1~12의 알콕시기이고; M은 0을 포함하는 양의 정수이다.)
An etchant composition having excellent selectivity for a silicon nitride film, characterized in that it comprises an inorganic acid solvent, a silane inorganic acid salt represented by the following [Formula 1], and an additive.
[Formula 1]
(In Formula 1, R 1 to R 5 are each hydrogen, halogen, a C1 to C12 alkyl group, and a C1 to 12 alkoxy group; M is a positive integer including 0.)
According to claim 1, wherein the content of the inorganic acid solvent is 80 to 99.9% by weight of the total weight of the composition, the content of the silane inorganic acid salt is 0.01 to 8% by weight, the content of the additive is 0.01 to 12% by weight An etchant composition having excellent selectivity to a silicon nitride film.
The etchant composition of claim 1 or 2, wherein the inorganic acid solvent is at least one selected from sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, and perchloric acid. .
[화학식 2]
The method according to claim 1 or 2, wherein the inorganic silane acid salt is prepared by reacting 100 parts by weight of a high concentration phosphoric acid of 99% or more containing polyphosphoric acid with 0.1 to 20 parts by weight of a silane compound represented by the following [Formula 2] An etchant composition having excellent selectivity to a silicon nitride film, characterized in that it is
[Formula 2]
[화학식 3]
(상기 화학식 3에서, OH기는 합성 조건에 따라 O- 또는 OH2가 될 수 있으며; R31 내지 R34는 각각 수소 원자, 할로겐 원자, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기 중에서 선택된 어느 하나이고; j, k, m, n은 각각 0을 포함하는 양의 정수이다.)
The method according to claim 1 or 2, wherein the inorganic silane acid salt is prepared by reacting 100 parts by weight of a high concentration phosphoric acid of 99% or more containing polyphosphoric acid with 0.1 to 20 parts by weight of a silane compound represented by the following [Formula 3] An etchant composition having excellent selectivity to a silicon nitride film, characterized in that it is
[Formula 3]
(In Formula 3, the OH group may be O − or OH 2 depending on synthesis conditions; R 31 to R 34 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. any one selected; j, k, m, and n are each a positive integer including 0.)
[화학식 4]
(상기 화학식 4에서, OH기는 합성 조건에 따라 O- 또는 OH2가 될 수 있으며; R41내지 R43은 각각 수소 원자, 할로겐 원자, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기 중에서 선택된 어느 하나이다.)
The method according to claim 1 or 2, wherein the inorganic silane acid salt is prepared by reacting 100 parts by weight of a high concentration phosphoric acid of 99% or more containing polyphosphoric acid with 0.1 to 20 parts by weight of a silane compound represented by the following [Formula 4] An etchant composition having excellent selectivity to a silicon nitride film, characterized in that it is
[Formula 4]
(In Formula 4, the OH group may be O − or OH 2 depending on synthesis conditions; R 41 to R 43 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. whichever one is chosen.)
The etchant composition of claim 1 or 2, wherein the additive is any one of ammonium chloride, aqueous ammonia, ammonium acetic acid, ammonium phosphate, and ammonium sulfate.
[화학식 1]
(상기 화학식 1에서, R1 내지 R5는 각각 수소, 할로겐, C1~C12의 알킬기, C1~12의 알콕시기이고; M은 0을 포함하는 양의 정수이다.)93 to 98% by weight of an aqueous solution of phosphoric acid having a degree of 83 to 87%, 0.2 to 3% by weight of a silane inorganic acid salt represented by the following [Formula 1], and 1 to 7% by weight of ammonium chloride, the silane inorganic acid salt Silver, an etchant composition having excellent selectivity for a silicon nitride film, characterized in that it is prepared by reacting 2 to 6 parts by weight of silicon dioxide (SiO 2 ) with 100 parts by weight of polyphosphoric acid having 2 to 5 phosphorus (P) atoms.
[Formula 1]
(In Formula 1, R 1 to R 5 are each hydrogen, halogen, a C1 to C12 alkyl group, and a C1 to 12 alkoxy group; M is a positive integer including 0.)
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| KR101539373B1 (en) | 2014-07-17 | 2015-07-27 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
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| KR20180075416A (en) * | 2016-12-26 | 2018-07-04 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
| KR20190038459A (en) * | 2017-09-29 | 2019-04-08 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
| KR102024758B1 (en) | 2018-05-26 | 2019-09-25 | 에스케이이노베이션 주식회사 | Etching composition, method for etching insulating layer of semiconductor devices, method for preparing semiconductor devices and silane compound |
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| KR101539373B1 (en) | 2014-07-17 | 2015-07-27 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
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