KR20200044426A - An etchant composition and a selecting method of silane coupling agent contained therein - Google Patents
An etchant composition and a selecting method of silane coupling agent contained therein Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 229910000077 silane Inorganic materials 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 150000004767 nitrides Chemical class 0.000 claims description 44
- 238000005530 etching Methods 0.000 claims description 40
- NIINUVYELHEORX-UHFFFAOYSA-N triethoxy(triethoxysilylmethyl)silane Chemical compound CCO[Si](OCC)(OCC)C[Si](OCC)(OCC)OCC NIINUVYELHEORX-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 3
- -1 Triethoxysilyl Chemical group 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 238000010187 selection method Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 description 13
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- HPEPIADELDNCED-UHFFFAOYSA-N triethoxysilylmethanol Chemical compound CCO[Si](CO)(OCC)OCC HPEPIADELDNCED-UHFFFAOYSA-N 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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Abstract
Description
본 발명은 식각액 조성물 및 이에 포함되는 실란계 커플링제의 선정 방법에 관한 것이다.The present invention relates to a method for selecting an etchant composition and a silane coupling agent included therein.
도 1을 참조하면, 3D NAND 플래시 메모리(flash memory) 제조 공정들 중 일부를 확인할 수 있다. 3D NAND 플래시 메모리는 산화물막 및 질화물막을 포함하는 다층막에서 질화물막만을 선택적으로 제거하는 공정(Wet removal of nitride)을 통해 제조될 수 있으며, 산화물막에는 손상을 주지 않으면서 질화물막을 완전히 제거하는 것이, 질화물막 제거 공정(Wet removal of nitride)의 핵심 기술 중 하나이다.Referring to FIG. 1, some of 3D NAND flash memory manufacturing processes may be identified. 3D NAND flash memory can be manufactured through a process of selectively removing only a nitride film from a multilayer film including an oxide film and a nitride film (Wet removal of nitride), and removing the nitride film completely without damaging the oxide film, It is one of the core technologies of the wet removal process.
일반적으로 질화물막 제거 공정에 사용되는 식각액 조성물은, 산화물막에는 손상을 주지 않으면서 질화물막만을 완전히 제거하는 효과를 얻기 위해, 방식 능력을 갖는 첨가제를 이용한다.In general, the etchant composition used in the nitride film removal process uses an additive having anticorrosive ability to obtain an effect of completely removing only the nitride film without damaging the oxide film.
그러나 산화물막에 손상을 주지 않는 범위 내에서 질화물막을 완전히 제거하려다 보니, 방식 능력이 강한 첨가제를 사용하게 되고, 따라서 질화물막이 완전히 제거되지 않는 공정 불량(도 2 참조)이 발생할 수 있다.However, since the nitride film is completely removed within a range that does not damage the oxide film, an additive having a strong anticorrosive ability is used, and thus a process defect in which the nitride film is not completely removed (see FIG. 2) may occur.
또는 질화물막을 완전히 제거하려다 보니, 방식 능력이 약한 첨가제를 사용하게 되고, 따라서 질화물막은 완전히 제거하였으나 산화물막에도 손상(damage)을 입히는 공정 불량(도 3 참조)이 발생할 수 있다.Alternatively, when trying to completely remove the nitride film, an additive having a weak anticorrosive ability is used, and thus, the nitride film is completely removed, but a process defect that damages the oxide film (see FIG. 3) may occur.
종래에는 산화물막 및 질화물막을 포함하는 다층막에서 질화물막만을 선택적으로 완전히 제거하기 위한, 적정 수준의 방식 능력을 갖는 첨가제를 선정함에 있어, 첨가제의 종류와 농도에 따라 실험적으로 확인하고 있다. 이러한 실험적 확인 없이 첨가제의 선별은 실질적으로 불가능하며, 이 때문에 식각액 조성물의 개발에 시간과 비용이 과도하게 소요된다는 문제가 있다.Conventionally, in selecting an additive having an appropriate level of anticorrosive ability to selectively remove only a nitride film from a multilayer film including an oxide film and a nitride film, it is experimentally confirmed according to the type and concentration of the additive. Screening of additives without such experimental confirmation is practically impossible, and thus, there is a problem that the development of the etchant composition takes excessive time and cost.
미국 공개특허 제2013-0092872호는 3D NAND 플래시 메모리의 제조 공정 중, 실리콘 산화물막 및 실리콘 질화물막에 대해 실리콘 질화물막만을 선택적으로 식각하는 식각액 조성물에 대해 개시하고 있으나, 구성 성분의 종류와 농도의 선정을 위해, 식각액 조성물의 식각 성능을 테스트가 불가피함을 확인할 수 있으며, 상술된 것과 같이, 식각액 조성물의 적정 조성을 찾는 데 시간과 비용이 과도하게 소요된다는 문제를 해결하고 있지 못한 실정이다.US Patent Publication No. 2013-0092872 discloses an etchant composition for selectively etching only a silicon nitride film with respect to a silicon oxide film and a silicon nitride film during the manufacturing process of a 3D NAND flash memory, but the type and concentration of components For selection, it can be confirmed that the test of the etching performance of the etchant composition is inevitable, and as described above, it has not solved the problem that it takes excessive time and money to find the proper composition of the etchant composition.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 별도의 실험적 확인 없이도, 산화물막 및 질화물막을 포함하는 다층막에서 질화물막만에 대한 선택적 식각 효과 및 방식 능력을 갖는 첨가제로서의 실란계 커플링제를 선별하기 위한 파라미터 및 이에 따른 실란계 커플링제를 포함하는 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is to improve the above-described problems of the prior art, and without additional experimental confirmation, a silane-based coupling agent as an additive having a selective etching effect and anti-corrosion ability for only the nitride film in a multilayer film including an oxide film and a nitride film An object of the present invention is to provide an etchant composition comprising a parameter for screening and thus a silane coupling agent.
또한, 본 발명은 산화물막 및 질화물막을 포함하는 다층막에서, 상기 질화물막만을 선택적으로 식각 가능한 것을 특징으로 하는 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etchant composition characterized in that only the nitride film can be selectively etched in a multilayer film including an oxide film and a nitride film.
또한, 본 발명은 상기 식각액 조성물을 이용하는 식각 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etching method using the etching solution composition.
또한, 본 발명은 상기 식각액 조성물이 포함하는 실란계 커플링제를 선택하는 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method for selecting a silane-based coupling agent included in the etching solution composition.
상기 목적을 달성하기 위해, 본 발명은, 인산, 실란(silane)계 커플링제 및 물을 포함하고, 상기 실란계 커플링제는, 반응 위치(active site)의 수를 가수분해(hydrolysis)된 형태의 분자량으로 나눈 뒤, 96.1을 곱하여 산출되는 Aeff 값이 2.2 이상 내지 4.0 이하의 범위를 만족시키는 것을 특징으로 하는 식각액 조성물을 제공한다. In order to achieve the above object, the present invention includes phosphoric acid, a silane-based coupling agent and water, and the silane-based coupling agent is in the form of hydrolysis of the number of active sites. After dividing by molecular weight, it provides an etchant composition characterized in that A eff calculated by multiplying 96.1 satisfies a range of 2.2 or more and 4.0 or less.
본 발명의 식각액 조성물은 산화물막 및 질화물막을 포함하는 다층막에서 질화물막만에 대한 선택적 식각 효과 및 방식 능력을 갖는 첨가제로서 실란계 커플링제를 별도의 실험적 확인 없이 선정할 수 있는 효과를 제공한다.The etching solution composition of the present invention provides an effect of selecting a silane-based coupling agent without additional experimental confirmation as an additive having a selective etching effect and anti-corrosion ability on only the nitride film in a multilayer film including an oxide film and a nitride film.
또한, 본 발명의 식각액 조성물은 산화물막에는 손상을 주지 않으면서 질화물막만을 선택적으로 식각하는 효과를 제공한다.In addition, the etching solution composition of the present invention provides an effect of selectively etching only the nitride film without damaging the oxide film.
도 1은 3D NAND 플래시 메모리(flash memory) 제조 공정들 중 일부를 나타내는 도면이다.
도 2 및 도 3은 3D NAND 플래시 메모리 제조 시, 질화물막 제거 공정(Wet removal of nitride) 중에 발생되는 공정 불량을 나타내는 도면이다.
도 4는 3D NAND 플래시 메모리 제조 공정 중 발생하는 부반응 산화물의 잔류 및 산화물막 손상 불량을 최소화할 수 있는, 실란계 커플링제 적정 방식 능력 범위를 나타내는 도면이다.
도 5는 실란계 커플링제의 Aeff 값과 식각 정도(etching amount)의 상관관계를 나타내는 그래프이다.1 is a diagram illustrating some of 3D NAND flash memory manufacturing processes.
2 and 3 are diagrams illustrating a process defect occurring during a wet removal of nitride during manufacturing of a 3D NAND flash memory.
FIG. 4 is a diagram showing a range of capabilities of an appropriate method for silane-based coupling agent to minimize residual oxide residue and damage to an oxide film during a 3D NAND flash memory manufacturing process.
FIG. 5 is a graph showing the correlation between the A eff value of the silane coupling agent and the etching amount.
본 발명은, 인산, 실란(silane)계 커플링제 및 물을 포함하고, 상기 실란계 커플링제는, 반응 위치(active site)의 수를 가수분해(hydrolysis)된 형태의 분자량으로 나눈 뒤, 96.1을 곱하여 산출되는 Aeff 값(하기 수식 참조)이 2.2 이상 내지 4.0 이하의 범위를 만족시키는 것을 특징으로 하는 식각액 조성물을 제공한다.The present invention includes phosphoric acid, a silane-based coupling agent and water, and the silane-based coupling agent divides the number of active sites by the molecular weight of the hydrolyzed form, and then 96.1. It provides an etchant composition characterized in that the multiplied A eff value (see the formula below) satisfies the range of 2.2 or more and 4.0 or less.
상기 실란계 커플링제의 Aeff 값은 2.2 이상 내지 4.0 이하의 범위를 만족시키는 것이 바람직하며, 2.2 이상 내지 3.0 이하의 범위를 만족시키는 것이 더욱 바람직하다. 상기 실란계 커플링제의 Aeff 값이 상기 범위 내로 포함될 경우, 상기 실란계 커플링제는 적정 수준의 방식 능력을 가질 수 있으며, 이를 통해, 비용과 시간이 소요되는 실제적 실험과정 없이도, 목적하는 방식 능력을 갖는 실란계 커플링제의 선별이 가능하다.It is preferable that the A eff value of the silane coupling agent satisfies the range of 2.2 or more and 4.0 or less, and more preferably satisfies the range of 2.2 or more and 3.0 or less. When the A eff value of the silane-based coupling agent is included within the above range, the silane-based coupling agent may have an appropriate level of anti-corrosion ability, and through this, without a costly and time-consuming practical experimentation process, the desired anti-corrosion ability It is possible to select a silane-based coupling agent having a.
상기 실란계 커플링제는 식각액 조성물의 산화물막인 SiO2 및 상기 산화물막 상의 질화물막인 SiN을 포함하는 다층막에 160℃에서 실란계 커플링제 농도 1000 ppm 기준, 10,000초 동안 처리한 경우, 식각 정도(etching amount, E/A)가 -20 Å 이상 내지 100 Å 이하의 범위를 만족하는 농도로 첨가되는 것이 바람직하고, 방식 능력은 상기 실란계 커플링제의 Aeff 값과 농도의 곱으로 연산되며, 식각 정도(etching amount, E/A)로 나타낼 수 있다. 식각 정도의 양의 값은 식각 공정 후 두께 증가를 의미하며, 음의 값은 두께 감소를 의미한다.When the silane coupling agent is treated with a silane-based coupling agent concentration of 1000 ppm at 160 ° C. for a multi-layered film including SiO 2 as an oxide film of the etchant composition and SiN as a nitride film on the oxide film, the etching degree ( Etching amount, E / A) is preferably added at a concentration satisfying the range of -20 20 or more to 100 Å or less, anti-corrosion ability is calculated as the product of A eff value and concentration of the silane-based coupling agent, etching It can be expressed as an etching amount (E / A). A positive value of the etching degree means an increase in thickness after the etching process, and a negative value means a decrease in thickness.
상기 식각액 조성물은 산화물막 및 질화물막을 포함하는 다층막에서, 상기 질화물막만을 선택적으로 식각하는 것을 특징으로 하며, 상기 산화물막은 SiO2을 포함하는 것이 바람직하고, 상기 질화물막은 SiN을 포함하는 것이 바람직하다.The etchant composition is characterized by selectively etching only the nitride film in a multilayer film including an oxide film and a nitride film, and the oxide film preferably contains SiO 2 , and the nitride film preferably contains SiN.
상기 식각액 조성물은 3D NAND 플래시 메모리 제조 공정에 이용되며, 상기 질화물막 제거 공정 중 발생하는, 부반응 산화물의 잔류 및 산화물막 손상 불량 문제를 최소화시킬 수 있다.The etchant composition is used in a 3D NAND flash memory manufacturing process, and it is possible to minimize the problem of residual residual oxides and defects in oxide film damage occurring during the nitride film removal process.
본 발명의 식각액 조성물은 상기 실란계 커플링제를 포함하여, 산화물막 및 질화물막을 포함하는 다층막에서 질화물막만을 선택적으로 식각함에 있어, 부반응 산화물의 잔류 시간이 길어져 질화물막이 완전히 제거되지 않는 불량(도 2 참조) 및 질화물막은 완전히 식각하였으나 산화물막에도 손상(damage)을 입혀 발생되는 공정 불량(도 3 참조)의 발생을 최소화할 수 있다. In the etching solution composition of the present invention, in the selective etching of only the nitride film in the multilayer film including the oxide film and the nitride film, including the silane-based coupling agent, the residence time of the side reaction oxide is long and the nitride film is not completely removed (FIG. 2) And the nitride film was completely etched, but the occurrence of process defects (see FIG. 3) caused by damaging the oxide film can be minimized.
부반응 산화물의 잔류 시간이 길어져 질화물막이 완전히 제거되지 않는 불량은 실란계 커플링제의 방식 능력이 적정 수준보다 강할 경우 발생되며, 산화물막 불량은 실란계 커플링제의 방식 능력이 적정 수준보다 약할 경우 발생된다.A defect in which the nitride film is not completely removed due to a long residence time of the side reaction oxide occurs when the anticorrosive ability of the silane coupling agent is stronger than an appropriate level, and an oxide film defect occurs when the anticorrosive ability of the silane coupling agent is weaker than an appropriate level. .
도 4를 참조하면, 실란계 커플링제의 Aeff가 붉은색 범위 내로 포함될 경우 (Aeff 3.0 이하), 부반응 산화물의 잔류 시간이 길어져 질화물막이 완전히 제거되지 않는 불량이 최소화되고, 실란계 커플링제의 Aeff이 녹색 범위 내로 포함될 경우 (Aeff 2.2 이상), 산화물막 손상 불량이 최소될 수 있다. 따라서, 붉은색 범위와 녹색 범위가 중첩되는 범위(Spec 만족 구간)의 방식 능력을 갖는 실란계 커플링제를 이용할 경우, 부반응 산화물의 잔류 시간이 길어져 질화물막이 완전히 제거되지 않는 불량 및 산화물막 손상 불량이 최소화될 수 있다.Referring to FIG. 4, when A eff of the silane coupling agent is included in the red range (A eff 3.0 or less), the residence time of the side reaction oxide is increased to minimize defects in which the nitride film is not completely removed, and the silane coupling agent is minimized. When Aeff is included in the green range (A eff 2.2 or higher), defects in oxide film damage can be minimized. Therefore, when a silane-based coupling agent having a corrosion resistance in a range in which the red range and the green range overlap (Spec satisfactory section) is used, the residence time of the side reaction oxide becomes long, and the defect that the nitride film is not completely removed and the defect of the oxide film damage are caused. Can be minimized.
이하에서, 본 발명의 식각액 조성물에 포함되는, 인산, 실란(silane)계 커플링제 및 물에 대해 보다 자세하게 설명한다.Hereinafter, phosphoric acid, a silane coupling agent and water included in the etching solution composition of the present invention will be described in more detail.
(A) 인산(A) Phosphoric acid
본 발명의 식각액 조성물에 포함되는 상기 인산(phosphoric acid)은 주산화제로서, 질화물막을 산화시키는 데 사용될 수 있다.The phosphoric acid (phosphoric acid) contained in the etching solution composition of the present invention is a main oxidizing agent, it can be used to oxidize the nitride film.
상기 인산의 함량은 조성물 총 중량에 대하여, 50 내지 95 중량%로 포함되며, 80 내지 90 중량%가 바람직하다. 상기 인산이 상기 함량 범위 내로 포함되는 경우, 적절한 식각 속도와 SiN/SiO 선택비를 높일 수 있다.The phosphoric acid content is contained in 50 to 95% by weight, based on the total weight of the composition, 80 to 90% by weight is preferred. When the phosphoric acid is included within the content range, an appropriate etching rate and a SiN / SiO selectivity may be increased.
(B) 실란계 커플링제(B) Silane coupling agent
본 발명의 식각액 조성물에 포함되는 상기 실란(silane)계 커플링제는 방식제로서, 산화물막 및 질화물막을 포함하는 다층막에서 산화물막이 상기 인산에 의해 산화되는 것을 방지하는 데 사용될 수 있다.The silane-based coupling agent included in the etching solution composition of the present invention is an anticorrosive agent, and may be used to prevent an oxide film from being oxidized by the phosphoric acid in a multilayer film including an oxide film and a nitride film.
상기 실란계 커플링제는, 반응 위치(active site)의 수를 가수분해(hydrolysis)된 형태의 분자량으로 나눈 뒤, 96.1을 곱하여 산출되는 Aeff 값이 2.2 이상 내지 4.0 이하의 범위를 만족시키는 것이 바람직하며, 2.2 이상 내지 3.0 이하의 범위를 만족시키는 것이 더욱 바람직하다.The silane coupling agent, after dividing the number of the reaction site (active site) by the molecular weight of the hydrolyzed (hydrolysis) form, it is preferable that the A eff value calculated by multiplying 96.1 satisfies the range of 2.2 or more to 4.0 or less It is more preferable to satisfy the range of 2.2 or more and 3.0 or less.
상기 실란계 커플링제는, 식각액 조성물의 식각 정도(etching amount, E/A)가 -20 Å 이상 내지 100 Å 이하의 범위를 만족하는 농도로 첨가되는 것이 바람직하다.The silane-based coupling agent is preferably added in a concentration that satisfies the range of the etching amount (etching amount, E / A) of -20 Å or more to 100 Å or less of the etchant composition.
상기 실란계 커플링제는 Tetraethyl orthosilicate, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, (Triethoxysilyl)methanol, (Triethoxysilyl)methane 으로 이루어진 군으로부터 선택되는 1종 이상인 것이 바람직하며, bis(triethoxysilyl)methane, 및 (Triethoxysilyl)methanol, (Triethoxysilyl)methane 으로 이루어진 군으로부터 선택되는 1종 이상인 것이 더욱 바람직하고, (Triethoxysilyl)methane, (Triethoxysilyl)methanol이 가장 바람직하다.The silane coupling agent is preferably at least one selected from the group consisting of Tetraethyl orthosilicate, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, (Triethoxysilyl) methanol, (Triethoxysilyl) methane, bis (triethoxysilyl) methane, and More preferably, at least one selected from the group consisting of (Triethoxysilyl) methanol and (Triethoxysilyl) methane, and (Triethoxysilyl) methane and (Triethoxysilyl) methanol are most preferred.
상기 실란계 커플링제의 함량은 조성물 총 중량에 대하여, 0.01 내지 10 중량%로 포함되며, 0.01 내지 1.0 중량%가 바람직하다. 상기 실란계 커플링제가 상기 함량 범위 내로 포함되는 경우, 첨가제의 자체 겔화를 조절할 수 있고, 적절한 SiO 방식 및 SiN 식각 성능을 보인다.The content of the silane-based coupling agent is included in an amount of 0.01 to 10% by weight based on the total weight of the composition, and preferably 0.01 to 1.0% by weight. When the silane-based coupling agent is included within the content range, it is possible to control the gelation of the additive itself, and exhibits an appropriate SiO method and SiN etching performance.
(C) 물(C) water
본 발명의 식각액 조성물에 포함되는 상기 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water contained in the etching solution composition of the present invention may be deionized water for semiconductor processing, and preferably, the deionized water of 18 kPa / cm or more may be used.
상기 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다.The content of the water may be included as a residual amount to make the total weight of the composition 100% by weight.
또한, 본 발명은, 산화물막 및 질화물막을 포함하는 다층막에서, 상기 질화물막만을 선택적으로 식각하는 식각액 조성물의 실란계 커플링제를 선정하는 방법을 제공한다.In addition, the present invention provides a method for selecting a silane coupling agent of an etchant composition for selectively etching only the nitride film in a multilayer film including an oxide film and a nitride film.
상기 실란계 커플링제의 선정 방법은, 반응 위치(active site)의 수를 가수분해(hydrolysis) 형태의 분자량으로 나눈 뒤, 96.1을 곱하여 산출되는 Aeff 값이 2.2 이상 내지 4.0 이하의 범위를 만족시키는 실란계 커플링제를 선택하는 것을 특징으로 한다.In the method of selecting the silane coupling agent, after dividing the number of active sites by the molecular weight in the form of hydrolysis, A eff calculated by multiplying 96.1 to satisfy a range of 2.2 or more to 4.0 or less It is characterized by selecting a silane-based coupling agent.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.
실시예 및 비교예에 따른 식각액 조성물의 제조Preparation of etchant compositions according to Examples and Comparative Examples
하기 표 1을 참조하여, 실시예 및 비교예에 따른 식각액 조성물을 제조하였다.Referring to Table 1, an etchant composition according to Examples and Comparative Examples was prepared.
하기 표 2 및 도 5를 참조하면, 실시예 및 비교예에 따른 식각액 조성물을 이용하여, 산화물막인 SiO2 및 상기 산화물막 상의 질화물막인 SiN을 포함하는 다층막에 160℃에서 실란계 커플링제 0.1%를 10,000초 동안 처리한 경우, Aeff 값과 식각 정도(etching amount, E/A)가 선형적 상관관계를 갖는 것을 확인할 수 있다.Referring to Tables 2 and 5 below, using a etchant composition according to Examples and Comparative Examples, a silane-based coupling agent 0.1 at 160 ° C. to a multilayer film comprising SiO 2 as an oxide film and SiN as a nitride film on the oxide film. When% is processed for 10,000 seconds, it can be seen that A eff value and etching amount (E / A) have a linear correlation.
구체적으로, 실란계 커플링제로서, Aeff 값이 2.2 이상 내지 4.0 이하의 범위에 포함되는 물질들을 포함하는 실시예 1 내지 14는 식각 정도(etching amount, E/A)가 우수하여, 산화물막 손상 불량과 부반응 산화물의 잔류 시간이 길어져 질화물막이 완전히 제거되지 않는 불량을 막아주는 효과가 우수한 것으로 판단할 수 있다.Specifically, as examples of the silane coupling agent, Examples 1 to 14 including materials having an A eff value of 2.2 or more and 4.0 or less have excellent etching amount (E / A), and thus damage the oxide film. It can be determined that the effect of preventing defects in which the nitride film is not completely removed due to a long residence time of the defects and side reaction oxides is excellent.
반면, 실란계 커플링제로서, Aeff 값이 2.2 이상 내지 4.0 이하의 범위에 포함되지 않는 물질들을 포함하는 비교예 1 내지 11은 식각 정도가 좋지 않아 산화물막 손상 불량이 발생되는 것으로 판단할 수 있다.On the other hand, as the silane coupling agent, A eff value of Comparative Examples 1 to 11 including materials not included in the range of 2.2 or more and 4.0 or less can be judged to cause poor oxide film damage due to poor etching degree. .
일 예로, 하기 표 3을 참조하면, 실란계 커플링제로서 bis(triethoxysilyl)methane을 포함하는 실시예 1의 Aeff 값은, 반응 위치의 수 3을 가수분해된 형태의 분자량 172.2로 나눈 뒤, 96.1을 곱하여 산출될 수 있다.As an example, referring to Table 3 below, the A eff value of Example 1 including bis (triethoxysilyl) methane as a silane coupling agent is 96.1 after dividing the number 3 of the reaction sites by the molecular weight of the hydrolyzed form 172.2. It can be calculated by multiplying.
(hydrolysis)(hydrolysis)
본 발명에 따른 실시예 및 비교예의 실험 결과를 통해, 실란계 커플링제의, Aeff 값과 산화물막 및 질화물막을 포함하는 다층막에 대한 방식력 사이의 상관관계를 새롭게 도출하였다.Through the experimental results of Examples and Comparative Examples according to the present invention, a correlation between the silane coupling agent, A eff value, and anticorrosive power for a multilayer film including an oxide film and a nitride film was newly derived.
Claims (8)
상기 실란계 커플링제는, 반응 위치(active site)의 수를 가수분해(hydrolysis)된 형태의 분자량으로 나눈 뒤, 96.1을 곱하여 산출되는 Aeff 값이 2.2 이상 내지 4.0 이하의 범위를 만족시키는 것을 특징으로 하는 식각액 조성물.
Phosphoric acid, a silane-based coupling agent and water,
The silane coupling agent, after dividing the number of reaction sites (active site) by the molecular weight of the hydrolysis (hydrolysis) form, multiplied by 96.1 A eff value is calculated to satisfy the range of 2.2 or more to 4.0 or less Etching liquid composition.
상기 실란계 커플링제의 Aeff 값이 2.2 이상 내지 3.0 이하의 범위를 만족시키는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
An etchant composition, wherein the silane coupling agent has an A eff value of 2.2 or more and 3.0 or less.
상기 실란계 커플링제는, 식각액 조성물의 식각 정도(etching amount, E/A)가 -20 Å 이상 내지 100 Å 이하의 범위를 만족하는 농도로 첨가되는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
The silane-based coupling agent, the etching amount of the etching liquid composition (etching amount, E / A) is etchant composition, characterized in that added in a concentration satisfying a range of -20 Å or more to 100 내지 or less.
상기 실란계 커플링제는 Tetraethyl orthosilicate, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane 및 Triethoxysilyl)methanol, Triethoxysilyl)methane 으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
The silane coupling agent is Tetraethyl orthosilicate, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane and Triethoxysilyl) methanol, Triethoxysilyl) methane etching solution composition characterized in that at least one member selected from the group consisting of.
상기 식각액 조성물은 산화물막 및 질화물막을 포함하는 다층막에서, 상기 질화물막만을 선택적으로 식각하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
The etchant composition is an etchant composition characterized by selectively etching only the nitride film in a multilayer film including an oxide film and a nitride film.
상기 산화물막은 SiO2을 포함하고,
상기 질화물막은 SiN을 포함하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 5,
The oxide film includes SiO 2 ,
The nitride film is an etchant composition comprising SiN.
조성물 총 중량에 대하여,
인산 50 내지 95 중량%;
실란계 커플링제 0.01 내지 10 중량%; 및
물 잔량을 포함하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
With respect to the total weight of the composition,
50 to 95% by weight of phosphoric acid;
Silane-based coupling agent 0.01 to 10% by weight; And
Etching liquid composition comprising a residual amount of water.
반응 위치(active site)의 수를 가수분해(hydrolysis)된 형태의 분자량으로 나눈 뒤, 96.1을 곱하여 산출되는 Aeff 값이 2.2 이상 내지 4.0 이하의 범위를 만족시키는 실란계 커플링제를 선택하는 것을 특징으로 하는, 실란계 커플링제의 선정 방법.
In a multilayer film including an oxide film and a nitride film, as a silane coupling agent of an etchant composition for selectively etching only the nitride film,
After dividing the number of active sites by the molecular weight of the hydrolyzed form, it is characterized by selecting a silane coupling agent having an A eff value calculated by multiplying 96.1 to satisfy a range of 2.2 or more and 4.0 or less. Selection method of silane coupling agent to be made.
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| KR1020180125172A KR20200044426A (en) | 2018-10-19 | 2018-10-19 | An etchant composition and a selecting method of silane coupling agent contained therein |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023223936A1 (en) * | 2022-05-16 | 2023-11-23 | 関東化学株式会社 | Silicon nitride etching liquid composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130092872A1 (en) | 2011-10-18 | 2013-04-18 | Soulbrain Co., Ltd. | Compositions for etching and methods of forming a semiconductor device using the same |
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| JP4799332B2 (en) * | 2006-09-12 | 2011-10-26 | 株式会社東芝 | Etching solution, etching method, and electronic component manufacturing method |
| JP4983422B2 (en) * | 2007-06-14 | 2012-07-25 | 東ソー株式会社 | Etching composition and etching method |
| JP2012099550A (en) * | 2010-10-29 | 2012-05-24 | Sanyo Chem Ind Ltd | Etchant for silicon nitride |
| US9368647B2 (en) * | 2011-10-18 | 2016-06-14 | Samsung Electronics Co., Ltd. | Compositions for etching |
| US10269591B2 (en) * | 2013-10-23 | 2019-04-23 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method of selectively removing silicon nitride and single wafer etching apparatus thereof |
| KR101539375B1 (en) * | 2014-07-17 | 2015-07-27 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
| KR20160050536A (en) * | 2014-10-30 | 2016-05-11 | 램테크놀러지 주식회사 | Etchant compositions for nitride layers and methods of manufacturing semiconductor devices using the same |
| CN107345137A (en) * | 2016-05-04 | 2017-11-14 | Oci有限公司 | The etching solution of particle appearance can be suppressed |
| TW201802231A (en) * | 2016-07-04 | 2018-01-16 | Oci有限公司 | Etching solution for silicon nitride |
| US10995269B2 (en) * | 2016-11-24 | 2021-05-04 | Samsung Electronics Co., Ltd. | Etchant composition and method of fabricating integrated circuit device using the same |
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| US20130092872A1 (en) | 2011-10-18 | 2013-04-18 | Soulbrain Co., Ltd. | Compositions for etching and methods of forming a semiconductor device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023223936A1 (en) * | 2022-05-16 | 2023-11-23 | 関東化学株式会社 | Silicon nitride etching liquid composition |
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| SG10201909721VA (en) | 2020-05-28 |
| CN111073650B (en) | 2021-11-23 |
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