KR102282702B1 - Etching compositions, etching method and methods of manufacturing semiconductor devices using the same - Google Patents
Etching compositions, etching method and methods of manufacturing semiconductor devices using the same Download PDFInfo
- Publication number
- KR102282702B1 KR102282702B1 KR1020170094920A KR20170094920A KR102282702B1 KR 102282702 B1 KR102282702 B1 KR 102282702B1 KR 1020170094920 A KR1020170094920 A KR 1020170094920A KR 20170094920 A KR20170094920 A KR 20170094920A KR 102282702 B1 KR102282702 B1 KR 102282702B1
- Authority
- KR
- South Korea
- Prior art keywords
- etching
- formula
- etching composition
- present
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005530 etching Methods 0.000 title claims abstract description 134
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000004065 semiconductor Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- 239000010408 film Substances 0.000 claims description 35
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 24
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 21
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 15
- 238000001039 wet etching Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 2
- -1 bicyclo[2.1.1]hexyl Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical group [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- BYGXNRZZNBOSBD-UHFFFAOYSA-N dimethyl(diphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C)(C)C1=CC=CC=C1 BYGXNRZZNBOSBD-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L21/04—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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
Abstract
본 발명은 식각 조성물, 식각 방법 및 이를 이용한 반도체 소자의 제조 방법에 관한 것이며, 보다 상세하게는 반도체 제조 공정에서 습식 식각하는 경우, 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있는 고선택비의 화합물을 포함하는 식각 조성물 및 이 식각 조성물을 이용한 식각 공정을 포함하는 반도체 소자의 제조 방법에 관한 것이다.The present invention relates to an etching composition, an etching method, and a method of manufacturing a semiconductor device using the same, and more particularly, in the case of wet etching in a semiconductor manufacturing process, a high-selectivity that can selectively remove a nitride layer while minimizing an etching rate of an oxide layer It relates to an etching composition including the compound of the ratio and a method of manufacturing a semiconductor device including an etching process using the etching composition.
Description
본 발명은 식각 조성물, 식각 방법 및 이를 이용한 반도체 소자의 제조 방법에 관한 것이며, 보다 상세하게는 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있는 고선택비의 화합물을 포함하는 식각 조성물 및 이 식각 조성물을 이용한 식각 공정을 포함하는 반도체 소자의 제조 방법에 관한 것이다.The present invention relates to an etching composition, an etching method, and a method of manufacturing a semiconductor device using the same, and more particularly, an etching composition comprising a compound of high selectivity capable of selectively removing a nitride layer while minimizing an etching rate of an oxide layer; It relates to a method of manufacturing a semiconductor device including an etching process using the etching composition.
반도체 제조 공정에 있어서, 실리콘 산화막(SiO2) 등의 산화막 및 실리콘 질화막(SiNx) 등의 질화막은 대표적인 절연막으로 각각 단독으로, 또는 1층 이상의 막들이 교대로 적층되어 사용된다. 상기 실리콘 질화막은 실리콘 산화막, 폴리 실리콘막, 실리콘 웨이퍼 표면 등과 접촉하는 구조로CVD (Chemical vapor deposition) 공정을 통해서 증착되며, 이는 건식 식각 및 습식 식각을 통해서 제거되는데, 인산(phosphoric acid)을 이용한 습식 식각이 널리 이용되고 있다. In a semiconductor manufacturing process, an oxide film such as a silicon oxide film (SiO 2 ) and a nitride film such as a silicon nitride film (SiN x ) are used as representative insulating films, either singly or by alternately stacking one or more layers. The silicon nitride layer is deposited through a chemical vapor deposition (CVD) process in a structure in contact with a silicon oxide layer, a polysilicon layer, and the surface of a silicon wafer, and is removed through dry etching and wet etching. Etching is widely used.
상기 실리콘 질화막을 제거하기 위한 습식 식각 공정에서는 일반적으로 인산과 탈이온수(deionized water)의 혼합물이 사용되고 있다. 상기 탈이온수는 식각율 감소 및 산화막에 대한 식각 선택성의 변화를 방지하기 위하여 첨가되는 것이나, 공급되는 탈이온수의 양의 미세한 변화에도 질화막 식각 제거 공정에 불량이 발생하는 문제가 있다. 또한, 인산은 강산으로서 부식성을 가지고 있어 취급에 어려움이 있다.In a wet etching process for removing the silicon nitride layer, a mixture of phosphoric acid and deionized water is generally used. The deionized water is added to prevent a decrease in an etch rate and a change in etch selectivity for the oxide film, but there is a problem in that a defect occurs in the etching removal process of the nitride film even with a slight change in the amount of deionized water supplied. In addition, phosphoric acid is a strong acid and has a corrosive property, so it is difficult to handle.
본 발명은 반도체 공정에서 실리콘 산화막에 비해 실리콘 질화막에 대한 식각 선택비가 높은 식각 조성물을 제공하고자 한다.An object of the present invention is to provide an etching composition having a higher etch selectivity for a silicon nitride film than for a silicon oxide film in a semiconductor process.
본 발명은 실리콘 웨이퍼 식각시 실리콘 질화막 식각 속도가 향상된 식각 조성물을 제공하고자 한다.An object of the present invention is to provide an etching composition having improved silicon nitride etching rate when etching a silicon wafer.
본 발명은 상기 식각 조성물을 이용한 식각 방법을 제공하고자 한다.An object of the present invention is to provide an etching method using the etching composition.
본 발명은 상기 식각 조성물을 이용한 반도체 소자의 제조방법을 제공하고자 한다.An object of the present invention is to provide a method of manufacturing a semiconductor device using the etching composition.
본 발명이 해결하고자 하는 과제는 이에 한정되는 것이 아니며, 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위에서 다양하게 확장될 수 있다.The problem to be solved by the present invention is not limited thereto, and may be variously expanded without departing from the spirit and scope of the present invention.
본 발명의 일 구현예는 인산 및 하기 화학식 1로 표시되는 화합물을 포함하는 식각 조성물을 제공한다. One embodiment of the present invention provides an etching composition including phosphoric acid and a compound represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
n은 2 내지 500의 정수이고,n is an integer from 2 to 500,
R1 및 R2는 각각 독립적으로 수소 또는 C1~C10의 알킬기이고, R1 및 R2 중 적어도 하나는 C1~C10의 알킬기이고,R 1 and R 2 are each independently hydrogen or a C 1 ~ C 10 alkyl group, and at least one of R 1 and R 2 is a C 1 ~ C 10 alkyl group,
L1은 단일결합 또는 -[C(R3)(R4)]p-이고, L 1 is a single bond or -[C(R 3 )(R 4 )] p -,
L2는 단일결합 또는 -[C(R5)(R6)]q-이고, L 2 is a single bond or -[C(R 5 )(R 6 )] q -,
p 및 q는 1 내지 4 의 정수이고,p and q are integers from 1 to 4,
R3 내지 R6은 각각 독립적으로 수소 또는 C1~C10의 알킬기이고, R4 및 R5는 서로 결합하여 치환 또는 비치환된 5원 내지 8원 고리를 형성할 수 있다. R 3 to R 6 are each independently hydrogen or a C 1 to C 10 alkyl group, and R 4 and R 5 may be bonded to each other to form a substituted or unsubstituted 5- to 8-membered ring.
본 발명의 다른 구현예는 상기 식각 조성물을 이용한 식각 방법을 제공한다.Another embodiment of the present invention provides an etching method using the etching composition.
본 발명의 다른 구현예는 상기 식각 조성물을 이용하여 수행되는 식각 공정을 포함하는 반도체 소자의 제조 방법을 제공한다.Another embodiment of the present invention provides a method of manufacturing a semiconductor device including an etching process performed using the etching composition.
본 발명은 인산에 상기 화학식 1로 표시되는 화합물을 첨가 한 식각 조성물을 제공함으로써, 실리콘 산화막의 식각을 억제하고 실리콘 질화막을 선택적으로 식각할 수 있다.The present invention can suppress the etching of the silicon oxide layer and selectively etch the silicon nitride layer by providing an etching composition in which the compound represented by Formula 1 is added to phosphoric acid.
본 발명의 식각 조성물은 고온 안정성이 뛰어나고, 파티클 발생을 방지하여 소자 특성을 향상시킬 수 있다. The etching composition of the present invention has excellent high-temperature stability and may prevent particle generation to improve device characteristics.
또한 본 발명의 식각 조성물을 이용한 식각 방법은, 인산의 반복 사용을 가능하게 하여 공정 비용을 감소시킬 수 있다.In addition, the etching method using the etching composition of the present invention can reduce the process cost by enabling the repeated use of phosphoric acid.
종래에는 인산(H3PO4)에 불산(HF) 또는 질산(HNO3) 등을 포함하는 식각 조성물을 이용하여 질화막을 제거하는 기술이 공지되었으나, 오히려 산화막의 식각 속도 증가로 질화막과 산화막의 식각 선택비를 저해시키는 문제가 나타나게 된다. Conventionally, a technique for removing a nitride layer using an etching composition containing phosphoric acid (H 3 PO 4 ), hydrofluoric acid (HF), nitric acid (HNO 3 ), etc. has been known, but rather, the etching of the nitride layer and the oxide layer is increased due to the increase in the etching rate of the oxide layer. Problems that impede the selection ratio appear.
또한 실리콘을 함유한 식각 조성물을 추가하는 경우 질화막과 산화막의 식각 선택비가 증가하지만, 인산안에 있는 실리콘 화합물과 식각 후에 나오는 실리콘 불순물이 만나서 파티클을 생성하며, 생성된 파티클이 웨이퍼 위에 증착이 되면서 불량을 일으키는 문제점이 있다. In addition, when an etching composition containing silicon is added, the etching selectivity of the nitride film and the oxide film increases, but the silicon compound in phosphoric acid meets the silicon impurity that comes out after etching to generate particles, and the generated particles are deposited on the wafer to prevent defects. There is a problem that causes
현재 알려진 바에 의하면 실리콘을 함유한 식각 조성물을 이용하여 식각을 한 경우, 후에 나오는 불산물이 규산(silicic acid)이다. 규산은 인산안에서 일정 농도로 올라 갈 경우에 파티클이 되어 필터에 걸리거나 웨이퍼 위에 증착 되기 때문에 어떻게 파티클을 줄일지에 대하여 많은 연구가 진행 중이다. According to what is currently known, when etching is performed using an etching composition containing silicon, the hydrofluoric acid produced later is silicic acid. When silicic acid rises to a certain concentration in phosphoric acid, it becomes a particle and gets caught on a filter or deposited on a wafer, so there are many studies on how to reduce particles.
따라서, 상기 문제점을 극복하여 실리콘 산화막에 대해 실리콘 질화막을 선택적으로 식각하며, 고온 안정성이 뛰어나고, 파티클 발생을 방지하는 새로운 조성의 식각 조성물이 필요한 실정이다.Therefore, there is a need for an etching composition having a new composition that selectively etches a silicon nitride film with respect to a silicon oxide film by overcoming the above problems, has excellent high-temperature stability, and prevents generation of particles.
이하, 본 발명에 대하여 상세하게 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현 가능하다.The present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms.
아래 열거된 정의는 본 발명을 기술하기 위해 사용된 다양한 용어들의 정의이다. 이들 정의는 달리 제한되지 않는 한, 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다.The definitions listed below are definitions of various terms used to describe the present invention. These definitions are used only to describe specific embodiments, and are not intended to limit the invention unless otherwise limited.
본 발명에서의 용어 “알킬”은 특별한 언급이 없는 한 탄소수 1 내지 10개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기이며, 직쇄 또는 측쇄 알킬기는 이의 주쇄에 10개 이하(예를 들어, C1-C10의 직쇄, C3-C10의 측쇄), 바람직하게는 4개 이하, 보다 바람직하게는 3개 이하의 탄소 원자를 가진다. “알킬”의 예로는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, sec-부틸, tert-부틸, 펜틸, 헥실 등이 있으나, 이에 한정되지 않는다.The term "alkyl" in the present invention is a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 10 carbon atoms, unless otherwise specified, and the straight or branched chain alkyl group has 10 or less in its main chain (e.g., C 1 -C 10 straight chain, C 3 -C 10 branched chain), preferably 4 or less, more preferably 3 or less carbon atoms. Examples of “alkyl” include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and the like.
본 발명에서의 용어 "시클로알킬"은 특별한 언급이 없는 한 탄소수 3 내지 10개의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 고리형의 포화 탄화수소를 의미한다. 이러한 시클로알킬의 예로는 시클로프로필, 시클로펜틸, 시클로헥실, 바이시클로[2.1.1]헥실, 바이시클로[2.2.1]헵틸 등이 있으나, 이에 한정되지 않는다. 본 발명에서 시클로알킬은 이의 고리 구조에 3,4,5,6 또는 7개의 탄소원자를 가질 수 있다. The term "cycloalkyl" in the present invention means a cyclic saturated hydrocarbon derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms unless otherwise specified. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, and the like. Cycloalkyl in the present invention may have 3,4,5,6 or 7 carbon atoms in its ring structure.
본 발명에서의 용어 “치환 또는 비치환”은 특별한 언급이 없는 한 중수소, 할로겐기, 알킬기 및 시클로알킬기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미하며, 바람직하게는 중수소 또는 알킬기가 1개 이상의 치환기로 치환 또는 비치환된 것을 의미하나, 이에 한정되지 않는다.In the present invention, the term “substituted or unsubstituted” is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, a halogen group, an alkyl group and a cycloalkyl group, or two or more of the substituents exemplified above, unless otherwise specified. It means substituted or unsubstituted in which a substituent is connected, and preferably means that deuterium or an alkyl group is substituted or unsubstituted by one or more substituents, but is not limited thereto.
본 발명에서의 용어 “고리”는 탄소수 5 내지 8개의 고리 원자를 가지는 1가의 지방족 탄화수소기를 의미하며, 단일 고리 또는 2이상의 고리의 축합 고리일 수 있다. The term “ring” in the present invention refers to a monovalent aliphatic hydrocarbon group having 5 to 8 ring atoms, and may be a single ring or a condensed ring of two or more rings.
본 발명은 인산 및 하기 화학식 1로 표시되는 화합물을 포함하는 식각 조성물을 제공한다.The present invention provides an etching composition comprising phosphoric acid and a compound represented by Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에서, n은 2 내지 500 의 정수이고, R1 및 R2는 각각 독립적으로 수소 또는 C1~C10의 알킬기이고, R1 및 R2 중 적어도 하나는 C1~C10의 알킬기이고, L1은 단일결합 또는 -[C(R3)(R4)]p-이고, L2는 단일결합 또는 -[C(R5)(R6)]q-이며, p 및 q는 1 내지 4 의 정수이고, R3 내지 R6은 각각 독립적으로 수소 또는 C1~C10의 알킬기이고, R4 및 R5는 서로 결합하여 치환 또는 비치환된 5원 내지 8원 고리를 형성할 수 있다. In Formula 1, n is an integer of 2 to 500, R 1 and R 2 are each independently hydrogen or a C 1 to C 10 alkyl group, and at least one of R 1 and R 2 is a C 1 to C 10 alkyl group and L 1 is a single bond or -[C(R 3 )(R 4 )] p -, L 2 is a single bond or -[C(R 5 )(R 6 )] q -, p and q are an integer of 1 to 4, R 3 to R 6 are each independently hydrogen or a C 1 to C 10 alkyl group, and R 4 and R 5 are bonded to each other to form a substituted or unsubstituted 5- to 8-membered ring. can
본 발명의 일 구현예에서, R3 및 R4는 각각 독립적으로 C1~C5의 알킬기이거나 치환 또는 비치환된 5원 내지 8원 고리를 형성할 수 있으며, 바람직하게는 R3 및 R4는 서로 결합하여 치환 또는 비치환된 5원 내지 6원 고리를 형성할 수 있다. In one embodiment of the present invention, R 3 and R 4 are each independently a C 1 ~ C 5 alkyl group or may form a substituted or unsubstituted 5 to 8 membered ring, preferably R 3 and R 4 may combine with each other to form a substituted or unsubstituted 5- to 6-membered ring.
본 발명의 일 구현예에 따르면, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다. According to one embodiment of the present invention, the compound represented by the formula (1) may be a compound represented by the following formula (2).
[화학식 2][Formula 2]
상기 화학식 2에서, n, R1 및 R2 각각은 화학식 1에서 정의된 바와 같다.In Formula 2, each of n, R 1 and R 2 is as defined in Formula 1.
본 발명의 일 구현예에서, R1 및 R2는 각각 독립적으로 C1~C10의 알킬기인 식각 조성물 일 수 있으며, 바람직하게는 R1 및 R2는 각각 독립적으로 메틸기, 에틸기, 프로필기, 부틸기 및 펜틸기 이루어진 군에서 선택될 수 있다.In one embodiment of the present invention, R 1 and R 2 may each independently be a C 1 to C 10 etchant composition, preferably R 1 and R 2 are each independently a methyl group, an ethyl group, a propyl group, It may be selected from the group consisting of a butyl group and a pentyl group.
본 발명의 일 구현예에서, 상기 화학식 1로 표시되는 화합물은 하기 화학식3 또는 4로 표시되는 식각 조성물일 수 있다: In one embodiment of the present invention, the compound represented by Formula 1 may be an etching composition represented by Formula 3 or 4:
[화학식 3] [Formula 3]
[화학식 4][Formula 4]
상기 화학식 3 또는 4에서, p는 2 내지 500의 정수이다.In Formula 3 or 4, p is an integer of 2 to 500.
본 발명의 일 구현예에 따라, 인산에 상기 화학식 1로 표시되는 화합물을 첨가 한 식각 조성물은 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있다. According to one embodiment of the present invention, the etching composition in which the compound represented by Formula 1 is added to phosphoric acid can selectively remove the nitride layer while minimizing the etching rate of the oxide layer.
더욱 구체적으로, 본 발명의 일 구현예 따르면, 상기 화학식 1의 화합물을 포함하는 식각 조성물의 실리콘 질화막의 식각 속도는 70 내지 150 Å/min 이며, 실리콘 산화막의 식각 속도는 0 내지 30 Å/min이다. 이 때, 본 발명의 실리콘 질화막/산화막 선택비는 20 이상을 가지게 되어, 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있게 한다.More specifically, according to an exemplary embodiment of the present invention, the etching rate of the silicon nitride layer of the etching composition including the compound of Formula 1 is 70 to 150 Å/min, and the etching rate of the silicon oxide layer is 0 to 30 Å/min. . At this time, the silicon nitride film/oxide film selectivity ratio of the present invention is 20 or more, so that the nitride film can be selectively removed while minimizing the etch rate of the oxide film.
또한 본 발명의 식각 조성물은 고온 안정성이 뛰어나고, 파티클 발생을 방지하여 소자 특성을 향상시킬 수 있다. In addition, the etching composition of the present invention has excellent high-temperature stability, and prevents the generation of particles to improve device characteristics.
반도체 소자 공정 중 웨이퍼 표면 위의 대표적인 오염물로 파티클을 들 수 있다. 종래 알려져 있는 실리콘을 함유한 식각 조성물의 식각 원리는 실리콘-히드록시 그룹을 실리콘-옥시즌-실리콘 형태로 변하게 하여 식각으로부터 일종의 보호막을 형성하게 만드는 것이다. 이 경우 산화막의 식각을 억제할 수 있지만, 인산 안에 있는 실리콘 화합물과 식각 후에 나오는 실리콘 불순물이 만나서 파티클이 쉽게 형성된다.Particles are a typical contaminant on the wafer surface during semiconductor device processing. The conventionally known etching principle of an etching composition containing silicon is to change a silicon-hydroxy group into a silicon-oxygen-silicon form to form a kind of protective layer from etching. In this case, the etching of the oxide film can be suppressed, but particles are easily formed because the silicon compound in phosphoric acid and the silicon impurity produced after etching meet.
이러한 문제를 피하기 위하여 실리콘-히드록시 그룹을 실리콘-옥시즌-카본으로 바꾸는 방법을 연구하였고, 본 발명의 화학식 1로 표시되는 화합물을 첨가 한 식각 조성물을 이용하면 실리콘-히드록시 그룹을 실리콘-옥시즌-실리콘 형태가 아닌 실리콘-옥시즌-카본의 형태로 변하게 하여 파티클 생성을 방지할 수 있다. 또한 인산 내에 실리콘이 없으므로 인산의 반복 사용을 가능하게 하여 공정 비용을 감소시킬 수 있다.In order to avoid this problem, a method for changing the silicon-hydroxy group into silicon-oxygen-carbon was studied, and when the etching composition added with the compound represented by Formula 1 of the present invention is used, the silicon-hydroxy group is converted to silicon-oxygen- It is possible to prevent the generation of particles by changing the form of silicon-oxygen-carbon rather than silicon form. In addition, since there is no silicon in the phosphoric acid, it is possible to use the phosphoric acid repeatedly, thereby reducing the process cost.
본 발명의 일 구현예에서, 상기 식각 조성물은, 상기 화학식 1로 표시되는 화합물을 20 내지 50000 PPM, 바람직하게는 1000 내지 20000 PPM 으로 포함할 수 있다.In an embodiment of the present invention, the etching composition may include the compound represented by Formula 1 in an amount of 20 to 50000 PPM, preferably 1000 to 20000 PPM.
상기 화학식 1로 표시되는 화합물의 함량이 20 PPM 미만인 경우, 실리콘 질화막 식각 속도가 향상되지 않거나, 고온에서 식각 공정의 안정성이 유지되지 않아 이물질 발생의 우려가 있다.When the content of the compound represented by Formula 1 is less than 20 PPM, the silicon nitride layer etch rate is not improved or the stability of the etching process is not maintained at high temperatures, so there is a risk of generating foreign substances.
또한, 상기 화학식 1로 표시되는 화합물이 50000 PPM을 초과하여 투입되는 경우, 오히려 산화막의 식각 속도 증가로 질화막과 산화막의 식각 선택비를 저해시키는 문제가 나타나게 된다.In addition, when the compound represented by Formula 1 is added in excess of 50000 PPM, there is a problem in that the etching selectivity between the nitride layer and the oxide layer is inhibited due to an increase in the etching rate of the oxide layer.
본 발명의 일 구현예에 따르면, 상기 식각 조성물은 인산을 80 내지 90 중량%, 화학식 1로 표시되는 화합물을 20 내지 50000 PPM 으로 포함할 수 있다. According to one embodiment of the present invention, the etching composition may include 80 to 90 wt % of phosphoric acid and 20 to 50000 PPM of the compound represented by Formula 1 .
상기 식각 조성물은, 상기 인산을 80 내지 90 중량%, 바람직하게는 85 내지 90 중량%, 더욱 바람직하게는 85 내지 89 중량%로 포함할 수 있다. The etching composition may include 80 to 90% by weight of the phosphoric acid, preferably 85 to 90% by weight, and more preferably 85 to 89% by weight.
상기 인산을 80 중량% 미만으로 포함하는 경우, 이물질이 발생하거나 실리콘 질화막 식각 속도가 저하되어 질화막이 용이하게 제거되지 않을 우려가 있다.When the phosphoric acid is included in an amount of less than 80% by weight, there is a fear that foreign substances may be generated or the etching rate of the silicon nitride layer may be lowered, so that the nitride layer may not be easily removed.
또한, 상기 인산을 90 중량%를 초과하여 포함하는 경우, 인산의 농도가 지나치게 높아져 식각 효과가 더디게 된다. In addition, when the phosphoric acid is included in an amount exceeding 90% by weight, the concentration of phosphoric acid is excessively high, thereby slowing the etching effect.
따라서, 본 발명에 따른 중량% 및 PPM 범위로 인산 및 화학식 1로 표시되는 화합물을 포함하는 경우 식각 조성물은 반도체 공정시 적정 수준의 안정성을 유지하면서도 높은 실리콘 산화막/질화막 선택비 및 향상된 실리콘 질화막 식각 속도를 구현할 수 있어 안정적인 식각 공정을 가능하게 한다.Accordingly, when phosphoric acid and the compound represented by Formula 1 are included in the weight % and PPM ranges according to the present invention, the etching composition maintains an appropriate level of stability during semiconductor processing, while maintaining a high silicon oxide/nitride layer selectivity and an improved silicon nitride layer etch rate can be implemented, enabling a stable etching process.
본 발명의 일 구현예에서, 상기 식각 조성물은 불소계 화합물을 추가로 포함할 수 있다. 본 발명이 사용하는 불소계 화합물은 산화막의 식각을 최대한 억제하면서 질화막의 식각 속도를 증가시키므로, 선택비를 향상시키는 효과를 얻을 수 있다. In one embodiment of the present invention, the etching composition may further include a fluorine-based compound. Since the fluorine-based compound used in the present invention increases the etching rate of the nitride film while suppressing the etching of the oxide film as much as possible, the effect of improving the selectivity can be obtained.
상기 불소계 화합물은 불산(HF), 불화나트륨(NaF), 불화수소나트륨(NaHF2), 불화암모늄(NH4F), 불화수소암모늄(NH4HF2), 붕불화암모늄(NH4BF4), 불화칼륨(KF), 불화수소칼륨(KHF2), 불화알루미늄(AlF3), 불화붕소산(HBF4), 불화리튬(LiF), 붕불화칼륨(KBF4) 및 불화칼슘(CaF2)으로 이루어지는 군에서 선택되는 하나 이상의 화합물을 포함한다.The fluorine-based compound is hydrofluoric acid (HF), sodium fluoride (NaF), sodium hydrogen fluoride (NaHF 2 ), ammonium fluoride (NH 4 F), ammonium hydrogen fluoride (NH 4 HF 2 ), ammonium borofluoride (NH 4 BF 4 ) , potassium fluoride (KF), potassium hydrogen fluoride (KHF 2 ), aluminum fluoride (AlF 3 ), boronic acid (HBF 4 ), lithium fluoride (LiF), potassium borofluoride (KBF 4 ), and calcium fluoride (CaF 2 ) It contains one or more compounds selected from the group consisting of.
본 발명의 일 구현예에서, 상기 식각 조성물은 상기 식각 조성물 전체에 대하여 인산을 80 내지 90 중량%, 화학식 1 로 표시되는 화합물을 20 내지 50000 PPM, 및 불소계 화합물을 0.01 내지 1 중량%로 더 포함하는, 식각 조성물일 수 있다.In one embodiment of the present invention, the etching composition further comprises 80 to 90% by weight of phosphoric acid, 20 to 50000 PPM of the compound represented by Formula 1, and 0.01 to 1% by weight of a fluorine-based compound, based on the total amount of the etching composition which may be an etching composition.
본 발명의 일 구현예에서, 식각 속도 향상을 위한 첨가제가 추가로 포함되는 것을 특징으로 하는, 식각 조성물일 수 있다.In one embodiment of the present invention, it may be an etching composition, characterized in that the additive for improving the etching rate is further included.
상기 첨가제는 식각 성능을 향상시키기 위하여 당업계에서 통상적으로 사용되는 임의의 첨가제를 말하는데, 계면활성제, 금속 이온 봉쇄제, 부식 방지제 등이 있다.The additive refers to any additive commonly used in the art to improve etching performance, such as a surfactant, a metal ion sequestering agent, and a corrosion inhibitor.
특히, 식각 속도 향상을 위한 첨가제가 포함되는 경우, 상기 화학식 1로 표시되는 화합물을 1.5 중량% 이상 포함되는 것이 고선택비 구현 측면에서 바람직하다.In particular, when an additive for improving the etch rate is included, 1.5 wt % or more of the compound represented by Formula 1 is preferably included in terms of high selectivity.
본 발명의 다른 구현예에 따르면, 본 발명의 식각 조성물은 다음과 같이 제조할 수 있다.According to another embodiment of the present invention, the etching composition of the present invention may be prepared as follows.
상기 화학식 1로 표시되는 화합물을 인산에 첨가하여 식각 조성물을 제조한다. 이때 식각 조성물 내의 화학식 1로 표시되는 화합물의 농도는 20 내지 50000 PPM 이며, 바람직하게는 1000 내지 20000 PPM 이다. 상기 식각 조성물을 25 oC 내지 100 oC 에서 10분 내지 3시간 동안 교반시키며, 바람직하게는 65 oC 내지 85 oC에서 1시간 동안 교반한다. An etching composition is prepared by adding the compound represented by Formula 1 to phosphoric acid. At this time, the concentration of the compound represented by Formula 1 in the etching composition is 20 to 50000 PPM, preferably 1000 to 20000 PPM. The etching composition is stirred for 10 minutes to 3 hours at 25 o C to 100 o C, preferably 65 o C to 85 o C for 1 h.
본 발명의 또 다른 구현예는 상기 제조된 식각 조성물을 이용해서 실리콘 박막을 식각하는 방법을 제공한다. Another embodiment of the present invention provides a method of etching a silicon thin film using the prepared etching composition.
상기 방법은 웨이퍼를 준비하는 단계 및 상기 웨이퍼를 본 발명의 식각 조성물로 식각하는 단계를 포함한다. 상기 식각 조성물을 이용하여 웨이퍼를 10초 내지 10분, 바람직하게는 1분 내지 5분 동안 식각하며, 식각 후 물로 1초 내지 5분, 바람직하게는 10초 내지 1분 동안 세정한다. The method includes preparing a wafer and etching the wafer with an etching composition of the present invention. The wafer is etched for 10 seconds to 10 minutes, preferably 1 minute to 5 minutes using the etching composition, and after etching, the wafer is washed with water for 1 second to 5 minutes, preferably 10 seconds to 1 minute.
본 발명의 일 구현예는 상기 식각 조성물을 이용하여 실리콘 질화막, 실리콘 산화막 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나를 식각하는 단계를 포함하는 식각 방법을 제공한다. One embodiment of the present invention provides an etching method comprising etching any one selected from the group consisting of a silicon nitride layer, a silicon oxide layer, and a combination thereof using the etching composition.
본 발명의 일 구현예는 상기 식각 조성물을 이용하여 수행되는 식각 공정을 포함하는 반도체 소자의 제조 방법을 제공한다. One embodiment of the present invention provides a method of manufacturing a semiconductor device including an etching process performed using the etching composition.
본 발명은 상기 식각 공정은 실리콘 산화막에 대하여 실리콘 질화막을 선택적으로 식각하는 것이며, 145 내지 185의 온도에서 수행되는 것인 반도체 소자의 제조 방법 일 수 있으며, 그 외 공정은 통상 알려진 방법을 사용할 수 있으므로 자세한 설명은 생락하도록 한다. In the present invention, the etching process is to selectively etch a silicon nitride film with respect to a silicon oxide film, and may be a method of manufacturing a semiconductor device that is performed at a temperature of 145 to 185, and other processes may use commonly known methods. A detailed description is omitted.
이하에서는 본 발명의 구체적인 실시예들을 제시한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, specific embodiments of the present invention are presented. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.
[실시예][Example]
실시예Example 1 및 2: 1 and 2: 식각etching 조성물의 제조 Preparation of the composition
인산 85 중량%와 물 15 중량%을 포함하는 인산 수용액을 준비하였다. 그 후 식각 조성물 내의 농도가 10,000ppm이 되도록 표 1에 기재된 화학식 1의 화합물을 첨가하여 실시예 1내지 2 및 비교예 1 내지 3에 따른 식각 조성물을 제조하였다. An aqueous solution of phosphoric acid containing 85% by weight of phosphoric acid and 15% by weight of water was prepared. Thereafter, the etching compositions according to Examples 1 to 2 and Comparative Examples 1 to 3 were prepared by adding the compound of Formula 1 shown in Table 1 so that the concentration in the etching composition was 10,000 ppm.
이 때 실시예 1 및 실시예 2에 사용된 화학식 1의 화합물의 p값은 평균 250인 것으로 측정되었으며, 통상적으로 100에서 300사이에 90% 이상이 존재하는 것으로 확인되었다.At this time, the p value of the compound of Formula 1 used in Examples 1 and 2 was measured to be an average of 250, and it was confirmed that 90% or more was present between 100 and 300 in general.
디페닐디메틸포스포니움
Diphenyldimethylphosphonium
테트라에틸포스포니움
tetraethylphosphonium
테트라프로필포스포니움
tetrapropylphosphonium
[물성 측정][Measurement of physical properties]
상기 실시예 및 비교예에 따라 제조된 식각 조성물을 써머 산화막(써머 SiOX ) 에 대해 165 oC에서 1분간 식각하였다. The etching compositions prepared according to Examples and Comparative Examples were etched at 165 ° C for 1 minute with respect to the thermal oxide film (thermal SiO X ).
총 5회에 걸쳐 식각 속도를 측정하였으며 그 평균 결과값은 하기 [표 2]와 같다. The etching rate was measured a total of 5 times, and the average result value is shown in [Table 2] below.
상기 [표2]에 나타난 바와 같이, 실시예 1및 2의 식각 조성물은 실리콘 산화막에 대한 식각 속도가 매우 낮음을 알 수 있었다.As shown in [Table 2], it was found that the etching compositions of Examples 1 and 2 had a very low etching rate for the silicon oxide layer.
이에 반해 비교예 1 내지 3의 식각 조성물은 실리콘 산화막에 대한 식각 속도가 높은 것을 볼 수 있었다. On the other hand, the etching compositions of Comparative Examples 1 to 3 showed a high etching rate for the silicon oxide layer.
[식각 속도 측정][Etch rate measurement]
상기 실시예 및 비교예에 따라 제조된 식각 조성물을 식각 온도를 달리하면서 실리콘 질화막 기판을 넣어 식각을 진행하였다.The etching composition prepared according to the above Examples and Comparative Examples was etched by putting a silicon nitride film substrate at different etching temperatures.
실리콘 질화막은 식각 조성물에 넣기 전 평탄화 작업을 진행하였으며, 평탄화작업은 50질량% 불산을 15:1로 희석한 후 희석 불산에 30초간 담가 진행하였다.The silicon nitride film was planarized before being put into the etching composition, and the planarization operation was carried out by diluting 50% by mass of hydrofluoric acid to 15:1 and then immersing it in diluted hydrofluoric acid for 30 seconds.
식각 속도는 엘립소미트리(Nano-View, SE MG-1000; Ellipsometery)를 이용하여 실리콘 질화막을 300초 동안 식각한 후, 양 막의 식각 전의 두께와 식각 후의 두께의 차이를 식각 시간(분)으로 나누어 산출하였다.The etching rate was determined by etching the silicon nitride film for 300 seconds using an ellipsometer (Nano-View, SE MG-1000; Ellipsometery), and dividing the difference between the thickness before and after etching of both films by the etching time (minutes). calculated.
하기 표3에 시간에 따른 식각 속도의 결과값을 나타내었다.Table 3 below shows the results of the etching rate according to time.
식각 속도
(Å/min)nitride film
etch rate
(Å/min)
식각 속도
(Å/min)oxide film
etch rate
(Å/min)
selection fee
상기 [표3]에 나타난 바와 같이 실시예 1및 2의 식각 조성물은 질화막의 식각 속도가 증가하고 산화막의 식각 속도가 억제함을 알 수 있었다.As shown in [Table 3], it was found that the etching compositions of Examples 1 and 2 increased the etching rate of the nitride film and suppressed the etching rate of the oxide film.
이는 본 발명에 따른 식각 조성물의 높은 선택비(질화막 식각 속도/산화막 식각 속도)를 나타내는 것으로, 실리콘 식각 공정에서 본 발명의 효과를 확인할 수 있었다.This indicates a high selectivity (nitride layer etch rate/oxide layer etch rate) of the etching composition according to the present invention, confirming the effect of the present invention in the silicon etching process.
Claims (11)
하기 화학식 1로 표시되는 화합물을 포함하는, 식각 조성물:
[화학식 1]
상기 화학식 1에서,
n은 2 내지 500 의 정수이고,
R1 및 R2는 각각 독립적으로 수소 또는 C1~C10의 알킬기이고, R1 및 R2 중 적어도 하나는 C1~C10의 알킬기이고,
L1은 단일결합 또는 -[C(R3)(R4)]p-이고,
L2는 단일결합 또는 -[C(R5)(R6)]q-이고,
p 및 q는 1 내지 4 의 정수이고,
R3 내지 R6은 각각 독립적으로 수소 또는 C1~C10의 알킬기이고, R4 및 R5는 서로 결합하여 치환 또는 비치환된 5원 내지 8원 고리를 형성할 수 있다.
phosphoric acid; and
An etching composition comprising a compound represented by Formula 1 below:
[Formula 1]
In Formula 1,
n is an integer from 2 to 500,
R 1 and R 2 are each independently hydrogen or a C 1 ~ C 10 alkyl group, and at least one of R 1 and R 2 is a C 1 ~ C 10 alkyl group,
L 1 is a single bond or -[C(R 3 )(R 4 )] p -,
L 2 is a single bond or -[C(R 5 )(R 6 )] q -,
p and q are integers from 1 to 4,
R 3 to R 6 are each independently hydrogen or a C 1 to C 10 alkyl group, and R 4 and R 5 may be bonded to each other to form a substituted or unsubstituted 5- to 8-membered ring.
R4 및 R5는 서로 결합하여 치환 또는 비치환된 5원 내지 6원 고리를 형성하는 것인, 식각 조성물.
The method of claim 1,
R 4 and R 5 are bonded to each other to form a substituted or unsubstituted 5- to 6-membered ring, the etching composition.
상기 화학식 1로 표시되는 화합물이 하기 화학식 2로 표시되는 화합물인, 식각 조성물:
[화학식 2]
상기 화학식 2에서,
n, R1 및 R2 각각은 제1항에서 정의된 바와 같다.
The method of claim 1,
An etching composition wherein the compound represented by Formula 1 is a compound represented by Formula 2 below:
[Formula 2]
In Formula 2,
Each of n, R 1 and R 2 is as defined in claim 1.
R1 및 R2는 각각 독립적으로 C1~C10의 알킬기인, 식각 조성물.
4. The method of claim 3,
R 1 and R 2 are each independently a C 1 ~ C 10 alkyl group, the etching composition.
[화학식 3]
[화학식 4]
상기 화학식 3 또는 4에서,
p는 2 내지 500의 정수이다.
The etching composition of claim 1, wherein the compound represented by Formula 1 is represented by Formula 3 or 4 below:
[Formula 3]
[Formula 4]
In Formula 3 or 4,
p is an integer from 2 to 500;
화학식 1 로 표시되는 화합물을 20 내지 50000 PPM 으로 포함하는, 식각 조성물.
6. The method according to any one of claims 1 to 5,
An etching composition comprising the compound represented by Formula 1 in an amount of 20 to 50000 PPM.
상기 식각 조성물의 실리콘 질화막의 식각 속도는 70 내지 150 Å/min 이며, 실리콘 산화막의 식각 속도는 0 내지 30Å/min인, 식각 조성물.
6. The method according to any one of claims 1 to 5,
The etching rate of the silicon nitride layer of the etching composition is 70 to 150 Å/min, and the etching rate of the silicon oxide layer is 0 to 30 Å/min, the etching composition.
상기 식각 조성물의 실리콘 질화막/산화막 선택비는 20 이상인, 식각 조성물.
6. The method according to any one of claims 1 to 5,
The silicon nitride film / oxide film selectivity of the etching composition is 20 or more, the etching composition.
식각 속도 향상을 위한 첨가제를 추가로 포함하는, 식각 조성물.
6. The method according to any one of claims 1 to 5,
An etching composition further comprising an additive for improving the etching rate.
An etching method comprising the step of etching any one thin film selected from the group consisting of a silicon nitride film, a silicon oxide film, and a combination thereof using the etching composition according to any one of claims 1 to 5.
A method of manufacturing a semiconductor device comprising an etching process using the etching composition according to any one of claims 1 to 5.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170094920A KR102282702B1 (en) | 2017-07-26 | 2017-07-26 | Etching compositions, etching method and methods of manufacturing semiconductor devices using the same |
| CN201810734849.XA CN109216187B (en) | 2017-07-06 | 2018-07-06 | Etching composition, etching method, and method for manufacturing semiconductor device using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170094920A KR102282702B1 (en) | 2017-07-26 | 2017-07-26 | Etching compositions, etching method and methods of manufacturing semiconductor devices using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20190012043A KR20190012043A (en) | 2019-02-08 |
| KR102282702B1 true KR102282702B1 (en) | 2021-07-28 |
Family
ID=65365043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020170094920A Active KR102282702B1 (en) | 2017-07-06 | 2017-07-26 | Etching compositions, etching method and methods of manufacturing semiconductor devices using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102282702B1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1866957A1 (en) * | 2005-04-08 | 2007-12-19 | Sachem, Inc. | Selective wet etching of metal nitrides |
| JP6088999B2 (en) * | 2013-05-02 | 2017-03-01 | 富士フイルム株式会社 | Etching solution and etching solution kit, etching method using the same, and method for manufacturing semiconductor substrate product |
| WO2014178424A1 (en) * | 2013-05-02 | 2014-11-06 | 富士フイルム株式会社 | Etching method, etching solution used in same, etching solution kit, and method for manufacturing semiconductor substrate product |
| KR101733289B1 (en) * | 2015-06-26 | 2017-05-08 | 오씨아이 주식회사 | ETCHING SOLUTION FOR SiLICON NITRIDE LAYER |
| KR102545802B1 (en) * | 2015-12-04 | 2023-06-21 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
-
2017
- 2017-07-26 KR KR1020170094920A patent/KR102282702B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190012043A (en) | 2019-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10640706B2 (en) | Etching compositions and method of etching by using the same | |
| US6383410B1 (en) | Selective silicon oxide etchant formulation including fluoride salt, chelating agent, and glycol solvent | |
| KR101728951B1 (en) | Etching solution for silicon nitride layer | |
| KR101733289B1 (en) | ETCHING SOLUTION FOR SiLICON NITRIDE LAYER | |
| US20080203060A1 (en) | Etching method and etching composition useful for the method | |
| KR102311335B1 (en) | Etching compositions and etching method using the same | |
| KR101320416B1 (en) | A Composition for wet etching , and method of wet etching with the same | |
| KR101391605B1 (en) | A Composition for wet etching of silicon nitride or silicon oxide | |
| KR102484988B1 (en) | Composition for etching and manufacturing method of semiconductor device using the same | |
| KR101907637B1 (en) | Etchant composition with high selectivity to silicon nitride | |
| KR20190096785A (en) | High selectivity Etchant composition for Nitride etching | |
| KR20220073813A (en) | Etching composition and method for selectively removing silicon nitride during fabrication of semiconductor devices | |
| JP2022520655A (en) | Silicon nitride film etching composition | |
| KR102484977B1 (en) | Etching compositions and etching method using the same | |
| CN109216187B (en) | Etching composition, etching method, and method for manufacturing semiconductor device using same | |
| KR102276085B1 (en) | Etching compositions and etching method using the same | |
| EP1062682B1 (en) | Selective silicon oxide etchant formulation including fluoride salt, chelating agent and glycol solvent | |
| KR102282702B1 (en) | Etching compositions, etching method and methods of manufacturing semiconductor devices using the same | |
| KR102770063B1 (en) | Etchant composition for etching and method for etching semiconductor device using the same | |
| KR102071599B1 (en) | High selectivity Silicon Nitride Etchant composition | |
| KR102378930B1 (en) | Etchant composition for etching nitride layer and method of forming pattern using the same | |
| KR102311328B1 (en) | Silicon nitride film etching method and manufacturing method of semiconductor device using the same | |
| JP2021034737A (en) | Etching composition, etching method of insulating film using it, and manufacturing method of semiconductor element | |
| KR20190081344A (en) | Etching compositions and etching method using the same | |
| JP7561545B2 (en) | Etching composition, method for etching insulating film using same, and method for manufacturing semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 20170726 |
|
| PG1501 | Laying open of application | ||
| A201 | Request for examination | ||
| PA0201 | Request for examination |
Patent event code: PA02012R01D Patent event date: 20190402 Comment text: Request for Examination of Application Patent event code: PA02011R01I Patent event date: 20170726 Comment text: Patent Application |
|
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20210420 Patent event code: PE09021S01D |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 20210705 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20210722 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 20210723 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration | ||
| PR1001 | Payment of annual fee |
Payment date: 20220427 Start annual number: 4 End annual number: 4 |