KR101097277B1 - A Composition for wet etching - Google Patents
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- KR101097277B1 KR101097277B1 KR1020090095327A KR20090095327A KR101097277B1 KR 101097277 B1 KR101097277 B1 KR 101097277B1 KR 1020090095327 A KR1020090095327 A KR 1020090095327A KR 20090095327 A KR20090095327 A KR 20090095327A KR 101097277 B1 KR101097277 B1 KR 101097277B1
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Abstract
본 발명은 습식 식각용 조성물에 관한 것이다.The present invention relates to a composition for wet etching.
습식 Wet
Description
본 발명은 실리콘산화막의 식각율을 최소화 하면서 실리콘질화막을 선택적으로 제거할 수 있는 실리콘질화막 습식 식각용 조성물에 관한 기술이다.The present invention relates to a silicon nitride film wet etching composition capable of selectively removing a silicon nitride film while minimizing the etching rate of the silicon oxide film.
실리콘산화막(SiO2) 및 실리콘질화막(SiNx)은 반도체 제조공정에서 사용되는 대표적인 절연막으로 사용되며, 각각 단독으로 사용되거나 혹은 1층 이상의 실리콘산화막 및 1층 이상의 실리콘질화막이 교대로 적층되어 사용되기도 한다. 또한 상기 실리콘산화막 및 실리콘질화막은 금속 배선과 같은 도전성 패턴을 형성하기 위한 하드마스크(Hard mask)로서도 사용된다.The silicon oxide film (SiO 2 ) and the silicon nitride film (SiN x ) are used as representative insulating films used in semiconductor manufacturing processes, and may be used alone, or one or more layers of silicon oxide and one or more layers of silicon nitride are alternately stacked. do. In addition, the silicon oxide film and the silicon nitride film are also used as a hard mask for forming a conductive pattern such as metal wiring.
일반적으로 실리콘질화막을 제거하기 위해서 인산(Phosphoric acid)을 사용하고 있으나, 식각률이 감소하고 산화막에 대한 선택성이 변하는 것을 방지하기 위하여 순수(Deionized Water)를 공급해야 한다. 그러나, 공급하는 순수의 양이 약간만 변하여도 질화막 제거 불량이 발생하는 문제점이 있다.Generally, Phosphoric acid is used to remove the silicon nitride film, but pure water should be supplied to prevent the etching rate and the selectivity to the oxide film from changing. However, there is a problem that the nitride film removal failure occurs even if the amount of pure water supplied is slightly changed.
또한 인산 자체가 강산이므로 부식성이 가지고 있어 취급하기가 까다롭다. In addition, since phosphoric acid itself is a strong acid, it is corrosive and difficult to handle.
종래 기술에서 인산에 불화수소산 또는 질산 등을 혼합하여 식각 조성물을 제조하여 질화막을 제거하는 기술을 공지하고 있으나, 이는 오히려 질화막과 산화막을 선택도를 저해시키는 결과를 초래하며, 특히 인산에 불화수소산을 혼합하는 경우 공정 Batch수가 증가함에 따라 질화막과 산화막의 선택비가 크게 변화한다. 이 현상은 불화수소산이 공정상에서 증발하기 때문에 불화수소산의 농도변화가 생기기 때문이다(일본특개평 제9-45660호).In the prior art, there is known a technique for preparing an etching composition by mixing hydrofluoric acid or nitric acid with phosphoric acid to remove the nitride film. However, this results in a decrease in selectivity between the nitride film and the oxide film, and particularly hydrofluoric acid in phosphoric acid. In the case of mixing, as the number of process batches increases, the selectivity of the nitride film and the oxide film changes significantly. This phenomenon is because hydrofluoric acid evaporates in the process, so that a change in concentration of hydrofluoric acid occurs (Japanese Patent Laid-Open No. 9-45660).
인산과 규산염을 이용한 기술이 공지되어 있으나, 규산염은 기판에 영향을 줄 수 있는 파티클을 유발함으로써 오히려 반도체 공정에 적합하지 못한 문제점이 있다.Techniques using phosphoric acid and silicates are known, but silicates are not suitable for semiconductor processing by causing particles to affect the substrate.
또한 TEOS(Tetraethyl orthosilicate)의 용해도를 증가시키기 위해 용매로 에탄올을 사용하는 경우도 있으나 인산공정이 고온이기 때문에 공정상에서 에탄올이 물과 함께 소모되면서 반응이 종료된 후에는 실리콘화합물의 용해도가 떨어져 파티클을 유발하거나 배수관에 실리콘화합물이 남는 문제점도 있다.In addition, ethanol may be used as a solvent to increase the solubility of TEOS (Tetraethyl orthosilicate) .However, since the phosphate process is high temperature, the ethanol is consumed with water in the process, and after the reaction is completed, the solubility of the silicon compound is reduced. There is also a problem that causes the silicon compound in the drain pipe.
상기의 문제점을 해결하고자 본 발명은 실리콘산화막에 대한 식각율을 최소화 하고, 실리콘질화막을 선택적으로 제거할 수 있으며, 기판에 파티클이 잔존하지 않으며, 고온에서 안정한 실리콘질화막 습식 식각용 조성물을 제공하는데 그 목적이 있다.In order to solve the above problems, the present invention minimizes the etching rate for the silicon oxide film, selectively removes the silicon nitride film, particles do not remain on the substrate, and provides a silicon nitride film wet etching composition stable at high temperature. There is a purpose.
상기의 목적을 달성하고자 본 발명자들은 실리콘산화막의 식각을 최소화하고 실리콘질화막을 선택적으로 제거할 수 있는 실리콘질화막 습식 식각용 조성물을 개발하게 되었으며, 본 발명은 인산, 및 하기 화학식 1의 규소화합물과 화학식 2의 옥심화합물을 포함하는 실리콘질화막 습식 시각용 조성물을 제공한다.In order to achieve the above object, the present inventors have developed a silicon nitride film wet etching composition capable of minimizing the etching of the silicon oxide film and selectively removing the silicon nitride film, and the present invention relates to phosphoric acid, a silicon compound represented by Chemical Formula 1 Provided is a silicon nitride film wet visual composition comprising the oxime compound of 2.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[상기 화학식 1 및 2에서, R1, R2, R3 및 R4는 서로 독립적으로 수소, (C1- C20)알킬, (C1-C20)알콕시, (C2-C20)알케닐, (C3-C20)시클로알킬, 아미노(C1-C20)알킬, 아미노(C1-C10)알킬아미노(C1-C10)알킬, (C6-C20)아릴, (C1-C20)알킬카보닐, (C1-C20)알킬카보닐옥시 및 시아노(C1-C10)알킬로부터 선택된다.][In Formulas 1 and 2, R 1 , R 2 , R 3 and R 4 are independently of each other hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C2-C20) alkenyl, (C3- C20) cycloalkyl, amino (C1-C20) alkyl, amino (C1-C10) alkylamino (C1-C10) alkyl, (C6-C20) aryl, (C1-C20) alkylcarbonyl, (C1-C20) alkyl Selected from carbonyloxy and cyano (C1-C10) alkyl.]
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 인산, 상기 화학식 1의 규소화합물 및 화학식 2의 옥심화합물을 포함하는 실리콘질화막 습식 식각용 조성물을 제공하며, 자세하게는 상기 화학식 1의 규소화합물 0.01 내지 2 중량%와 상기 화학식 2의 옥심화합물 0.001 내지 1 중량%와 인산 97 내지 99.98 중량%를 포함하는 실리콘질화막 습식 식각용 조성물을 제공한다. 본 발명은 상기 화학식 1의 규소화합물과 화학식 2의 옥심화합물 및 인산을 0.01 ~ 2 중량% : 0.001 내지 1 중량% : 97 내지 99.98 중량%로 혼합하는 것이 실리콘산화막의 식각율을 최소화하고, 만족할만한 실리콘질화막의 식각율 및 식각속도를 확보할 수 있으며, 상기의 범위를 벗어나는 조성비로 혼합할 경우, 예를 들어, 규소화합물이 초과하면 실리콘산화막의 식각은 일어나지 않지만, 공정 후 과량의 규소화합물이 석출되거나, 실리콘질화막의 식각속도가 현저하게 떨어져서 공정이 비효율적, 비경제적이다. 또한 옥심화합물이 초과하여 사용하여도 특성에는 변화가 없기 때문에 비경제적이다.The present invention provides a silicon nitride film wet etching composition comprising phosphoric acid, the silicon compound of Formula 1 and the oxime compound of Formula 2, and in detail, 0.01 to 2% by weight of the silicon compound of Formula 1 and the oxime compound of Formula 2 It provides a silicon nitride film wet etching composition comprising 0.001 to 1% by weight and 97 to 99.98% by weight phosphoric acid. In the present invention, the silicon compound of Formula 1, the oxime compound of Formula 2, and phosphoric acid are mixed in an amount of 0.01 to 2% by weight: 0.001 to 1% by weight: 97 to 99.98% by weight to minimize the etching rate of the silicon oxide film, and satisfactory. Etching rate and etching rate of the silicon nitride film can be secured, and when mixed at a composition ratio outside the above range, for example, when the silicon compound is exceeded, the silicon oxide film is not etched, but excess silicon compound is precipitated after the process. Alternatively, the etching rate of the silicon nitride film is significantly lowered, which makes the process inefficient and economical. In addition, even if the oxime compound is used in excess, it is uneconomical because there is no change in properties.
상기 본 발명의 실리콘질화막 습식 식각용 조성물에 이용되는 인산 및 하기에 기재된 본 발명의 인산은 약 85 중량% 농도로 물에 녹아 있는 인산을 의미한다.The phosphoric acid used in the silicon nitride film wet etching composition of the present invention and the phosphoric acid of the present invention described below refer to phosphoric acid dissolved in water at a concentration of about 85% by weight.
본 발명의 상기 화학식 1의 규소화합물로는, 중심원자인 규소에 직접적으로 결합하는 치환기가 적어도 하나의 옥사이드를 포함하는 것이 실리콘산화막의 식각을 예방할 수 있으며, 구체적으로는 중심원자인 규소와 직접적으로 결합하는 치환기가 적어도 하나의 알콕시 또는 알킬카보닐옥시를 포함하는 것이 바람직하며, 보다 구체적으로는 중심원자인 규소와 직접적으로 결합하는 치환기가 적어도 하나의 메톡시, 에톡시 및 아세톡시로부터 선택되는 것을 포함하는 것이 바람직히다.As the silicon compound of Chemical Formula 1 of the present invention, the substituent that directly bonds to silicon, which is a central atom, includes at least one oxide, which may prevent etching of the silicon oxide film, and specifically, directly with silicon, which is a core atom. It is preferable that the substituents to be bonded include at least one alkoxy or alkylcarbonyloxy, and more specifically, that the substituents to directly bond with silicon, which is the central atom, are selected from at least one of methoxy, ethoxy and acetoxy. It is preferable to include.
본 발명의 상기 화학식 1의 규소화합물은 구체적인 예로서, 부틸(메톡시)디메틸실란, 3-시아노프로필디메틸메톡시실란, 트리메틸에톡시실란, 트리메틸메톡시실란, 헥실디메톡시실란, 메틸디에톡시실란, 4-아미노부틸디메틸메톡시실란, 3-아미노프로필디메틸에톡시실란, 부틸트리메톡시실란, 에틸트리에톡시실란, 이소부틸트리에톡시실란, 메틸트리메톡시실란, 테트라메톡시실란, 테트라에톡시실란, 트리에톡시실란, 부틸트리에톡시실란, 트리메틸펜틸실란, 3-(2-아미노에틸)아미노프로필트리메톡시실란 및 3-아미노프로필트리에톡시실란등으로부터 선택되는 것을 이용할 수 있으며, 상기 나열된 구체적인 예는 임의의 화합물을 예시한 것일 뿐, 이로 한정하는 것은 아니다.As a specific example, the silicon compound of Chemical Formula 1 of the present invention may include butyl (methoxy) dimethylsilane, 3-cyanopropyldimethylmethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, hexyldimethoxysilane, and methyldiethoxy. Silane, 4-aminobutyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, butyltrimethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, methyltrimethoxysilane, tetramethoxysilane, tetra Ethoxysilane, triethoxysilane, butyltriethoxysilane, trimethylpentylsilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like can be used. , The specific examples listed above are illustrative of any compound, but are not limited thereto.
본 발명의 상기 화학식 2의 옥심화합물은 구체적은 예로, 아세톤옥심, 2-부탄논 옥심, 아세트알데하이드옥심, 씨클로헥사논옥심, 아세토펜타논옥심, 씨클로데카논옥심으로부터 선택되는 1종 이상을 이용할 수 있다.Specific examples of the oxime compound of Formula 2 may include at least one selected from acetone oxime, 2-butanone oxime, acetaldehyde oxime, cyclohexanone oxime, acetopentanone oxime, and cyclodecanone oxime. have.
본 발명은 상기 인산, 화학식 1의 규소화합물 및 화학식 2의 옥심화합물을 포함하는 실리콘질화막 습식 식각용 조성물에 있어서, 실리콘질화막의 식각 속도를 향상시키기 위하여 무기산, 불소계첨가제 및 이들의 혼합물로부터 선택되는 첨가제 를 더 포함할 수 있다.The present invention is a silicon nitride film wet etching composition comprising the phosphoric acid, the silicon compound of Formula 1 and the oxime compound of Formula 2, the additive selected from inorganic acids, fluorine-based additives and mixtures thereof to improve the etching rate of the silicon nitride film It may further include.
본 발명은 상기 인산, 화학식 1의 규소화합물 및 화학식 2의 옥심화합물을 포함하는 실리콘질화막 습식 식각용 조성물에 있어서, 실리콘질화막의 식각 속도를 향상시키기 위하여 무기산을 더 첨가할 수 있으며, 상기 인산과 화학식 1의 규소화합물과 화학식 2의 옥심화합물을 포함하는 실리콘질화막 습식 식각용 조성물의 총 중량에 대하여 0.1 내지 10 중량%의 무기산을 더 포함할 수 있다. 상기 무기산으로는 질산, 황산 및 염산으로부터 선택되는 1종 이상을 이용할 수 있으며, 바람직하게는 황산이 좋다. 상기 무기산을 상기 인산과 화학식 1의 규소화합물을 포함하는 실리콘질화막 습식 식각용 조성물의 총 중량에 대하여 0.1 중량% 미만으로 투입할 경우, 실리콘질화막의 식각 속도가 향상되지 않으며, 10 중량%를 초과할 경우 실리콘질화막의 식각 속도는 더 이상 향상되지 않기 때문에 0.1 내지 10 중량%로 투입하는 것이 좋다.The present invention, in the silicon nitride film wet etching composition comprising the phosphoric acid, the silicon compound of Formula 1 and the oxime compound of Formula 2, an inorganic acid may be further added to improve the etching rate of the silicon nitride film, the phosphoric acid and the formula 0.1 to 10% by weight of the inorganic acid based on the total weight of the silicon nitride film wet etching composition including the silicon compound of Formula 1 and the oxime compound of Formula 2 may be further included. The inorganic acid may be one or more selected from nitric acid, sulfuric acid and hydrochloric acid, preferably sulfuric acid. When the inorganic acid is added at less than 0.1% by weight relative to the total weight of the silicon nitride film wet etching composition including the phosphoric acid and the silicon compound of Formula 1, the etching rate of the silicon nitride film does not improve, and may exceed 10% by weight. In this case, since the etching rate of the silicon nitride film is no longer improved, it is preferable to add 0.1 to 10% by weight.
본 발명은 상기 인산, 화학식 1의 규소화합물 및 화학식 2의 옥심화합물을 포함하는 실리콘질화물 습식 식각용 조성물에 있어서, 실리콘질화막의 식각 속도를 향상시키기 위하여 불소계 첨가제를 더 포함할 수 있으며, 자세하게는 상기 인산, 화학식 1의 규소화합물 및 화학식 2의 옥심화합물을 포함하는 실리콘질화물 습식 식각용 조성물의 총 중량에 대하여 0.001 내지 1 중량%의 불소계 첨가제를 더 포함할 수 있다. 상기 불소계 첨가제로는 불화수소, 불화암모늄 및 불화수소암모늄으로부터 선택되는 1종 이상을 이용할 수 있으며, 바람직하게는 불화수소암모늄이 좋다. 상기 불소계 첨가제를 인산, 화학식 1의 규소화합물 및 무기산을 포함하는 실 리콘질화물 습식 식각용 조성물에 대하여 0.001 중량% 미만으로 투입할 경우, 실리콘질화막의 식각 속도가 향상되지 않으며, 1 중량% 초과할 경우, 실리콘질화막의 식각 속도가 크게 향상되지만, 실리콘산화막 또한 식각량이 증가되면서 실리콘질화막과의 선택비가 감소되는 단점이 있다.The present invention, in the silicon nitride wet etching composition comprising the phosphoric acid, the silicon compound of formula (1) and the oxime compound of formula (2), may further comprise a fluorine-based additive to improve the etching rate of the silicon nitride film, in detail The fluorine-based additive may further include 0.001 to 1% by weight based on the total weight of the silicon nitride wet etching composition including phosphoric acid, the silicon compound of Formula 1, and the oxime compound of Formula 2. As the fluorine-based additive, one or more selected from hydrogen fluoride, ammonium fluoride, and ammonium hydrogen fluoride may be used, preferably ammonium hydrogen fluoride. When the fluorine-based additive is added in an amount less than 0.001% by weight relative to the silicon nitride wet etching composition including phosphoric acid, the silicon compound of Formula 1, and an inorganic acid, the etching rate of the silicon nitride film does not improve, and when it exceeds 1% by weight Although the etching rate of the silicon nitride film is greatly improved, the silicon oxide film also has a disadvantage in that the selectivity with the silicon nitride film is reduced as the etching amount is increased.
본 발명은 상기 인산, 화학식 1의 규소화합물 및 화학식 2의 옥심화합물을 포함하는 실리콘질화물 습식 식각용 조성물의 총 중량에 대하여, 상기 기술된 무기산 또는 불소계첨가제의 중량비로 무기산 및 불소계첨가제를 함께 혼합한 조성물을 실리콘질화막의 습식 식각용 조성물로 이용할 수 있다.The present invention relates to the total weight of the silicon nitride wet etching composition comprising the phosphoric acid, the silicon compound of the formula (1) and the oxime compound of the formula (2), by mixing the inorganic acid and fluorine-based additive in a weight ratio of the inorganic acid or fluorine-based additive described above The composition can be used as a wet etching composition of the silicon nitride film.
본 발명의 상기 실리콘질화막 습식 식각용 조성물은 반도체 공정에서 식각하고자 하는 실리콘질화막에 도포하기 전에 가열하여 이용하는 것이 보다 효과적인 식각 성능을 얻을 수 있으며, 구체적으로는 100 내지 180℃로 예열하여 이용하는 것이 바람직하다.The silicon nitride film wet etching composition of the present invention can be used by heating before applying to the silicon nitride film to be etched in the semiconductor process to obtain more effective etching performance, specifically, it is preferable to use by preheating to 100 to 180 ℃. .
본 발명의 실리콘질화막 습식 식각용 조성물은 실제 실리콘산화막과 실리콘질화막이 형성된 기판을 침지한 결과, 실리콘질화막의 에칭속도가 55 내지 300Å/min.으로 나타났고, 실리콘산화막의 에칭속도는 0.5 내지 1 Å/min.으로 나타났으며, 실리콘질화막 대 실리콘산화막의 선택도는 55 내지 ∞으로써, 실리콘산화막에 대한 식각율이 거의 제로(영)에 가까우면서도 실리콘질화막만을 식각할 수 있는 놀라운 효과를 볼 수 있었다. 또한 인산만을 식각액으로 사용할 경우, 공정 Batch수가 증가할수록 실리콘질화막의 식각율이 감소하는 문제점이 있으나, 본 발명에서는 실리콘질화막의 식각율이 공정 Batch에 따라서 변하지 않기 때문에 우수한 장점을 갖고 있다.In the silicon nitride film wet etching composition of the present invention, as a result of immersing the substrate on which the silicon oxide film and the silicon nitride film were formed, the etching rate of the silicon nitride film was found to be 55 to 300 Pa / min., And the etching rate of the silicon oxide film was 0.5 to 1 Pa. / min., and the selectivity of silicon nitride to silicon oxide was 55 to ∞, and the etch rate for the silicon oxide was almost zero, and the silicon nitride could be etched. . In addition, when only phosphoric acid is used as an etching solution, the etching rate of the silicon nitride film decreases as the number of process batches increases. However, in the present invention, the etching rate of the silicon nitride film does not change depending on the process batch.
따라서, 본 발명의 상기 실리콘질화막 습식 식각용 조성물은 실리콘질화막층과 실리콘산화막층이 혼재할 경우, 실리콘산화막에 대하여 식각 영향을 거의 끼치지 않으면서 실리콘질화막만을 식각하여 제거하는데 놀라운 효과를 발휘한다.Therefore, when the silicon nitride film wet etching composition of the present invention is mixed with the silicon nitride film layer and the silicon oxide film layer, the silicon nitride film wet etching composition has a surprising effect in etching and removing only the silicon nitride film with little etching effect on the silicon oxide film.
본 발명에 따르면 특정한 실리콘화합물과 옥심화합물 및 인산을 포함하는 조성물을 실리콘질화막 식각액으로 사용함으로써, 실리콘 질화막 및 실리콘 산화막층이 혼재할 경우, 실리콘 신화막에 대하여 식각 영향을 거의 끼치지 않으면서 실리콘 질화막만을 식각하는 효과를 볼 수 있다. 또한 통상적으로 사용하는 에칭액에 비하여 높은 식각률과 선택도를 얻을 수 있으며 장시간 사용함에 있어 기존 에칭액 대비 실리콘 질화막의 에칭속도 저하의 문제점이 발생되지 않아 실리콘질화막의 선택적 에칭이 필요한 반도체 소자 제조시에 효과적으로 적용될 수 있다. According to the present invention, by using a composition containing a specific silicon compound, an oxime compound, and phosphoric acid as a silicon nitride film etching solution, when the silicon nitride film and the silicon oxide film layer are mixed, the silicon nitride film has little effect on etching the silicon nitride film. You can see the effect of etching only. In addition, high etching rate and selectivity can be obtained compared to the etching solution used in general, and it can be effectively applied in the manufacture of semiconductor devices requiring selective etching of the silicon nitride film since the problem of lowering the etching rate of the silicon nitride film compared to the conventional etching solution does not occur. Can be.
이하, 본 발명을 하기의 실시예에 의거하여 좀 더 상세히 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 한정하지는 않는다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.
실시예Example
실시예는 비이커에 실리콘질화막 습식 식각 조성물을 투입하고 157℃ 또는 165℃ 온도에 도달했을 때, 실시하였으며, 실리콘질화막이 형성된 기판을 가열된 식각 조성물에 10분간 침지하였으며, 실리콘열산화막이 형성된 기판을 침지하여 선 택도를 측정하였다.An embodiment was performed when the silicon nitride film wet etching composition was added to a beaker and reached a temperature of 157 ° C. or 165 ° C., and the substrate on which the silicon nitride film was formed was immersed in the heated etching composition for 10 minutes. The selectivity was measured by immersion.
비교예 1 및 2는 실리콘질화막이 형성된 기판을 인산에 투입하여 질화막과 산화막을 식각 속도 및 선택도를 측정하였으며, 실시예 1은 인산, 규소화합물(테트라메톡시실란) 및 옥심화합물(아세톤 옥심), 실시예 2는 인산, 규소화합물(테트라에톡시실란) 및 옥심화합물(2-부타논옥심) 실시예 3 및 4는 인산, 규소화합물(테트라에톡시실란; TEOS), 옥심화합물(아세톤 옥심) 및 황산, 실시예 5는 인산, 규소화합물(테트라에톡시실란), 옥심화합물(아세톤 옥심), 황산 및 불화수소암모늄, 실시예 6은 인산, 규소화합물(테트라에톡시실란), 옥심화합물(아세톤 옥심) 및 불화수소암모늄(ABF; Amoonium Bifluoride)을 각각 식각 조성물로 하여 식각 속도 및 선택도를 측정하였다.In Comparative Examples 1 and 2, the silicon nitride film-formed substrate was added to phosphoric acid, and the etching rate and selectivity of the nitride film and the oxide film were measured. Example 2 is phosphoric acid, silicon compound (tetraethoxysilane) and oxime compound (2-butanone oxime) Examples 3 and 4 are phosphoric acid, silicon compound (tetraethoxysilane; TEOS), oxime compound (acetone oxime) And sulfuric acid, Example 5 is phosphoric acid, silicon compound (tetraethoxysilane), oxime compound (acetone oxime), sulfuric acid and ammonium bifluoride, Example 6 is phosphoric acid, silicon compound (tetraethoxysilane), oxime compound (acetone Etch rate and selectivity were measured using oxime) and ammonium bifluoride (ABF; Amoonium Bifluoride) as an etching composition, respectively.
상기 비교예 1 및 실시예 1 내지 6에서, 질화막 및 산화막의 식각 속도 및 선택도는 하기에 보다 상세하게 설명한다.In Comparative Example 1 and Examples 1 to 6, the etching rate and selectivity of the nitride film and the oxide film will be described in more detail below.
<평가><Evaluation>
식각속도는 엘립소미트리(Nano-View사, SE MG-1000; Ellipsometery)를 이용하여 실리콘 질화막 및 산화막의 두께를 측정함으로써 평가하였다. The etch rate was evaluated by measuring the thickness of the silicon nitride film and the oxide film using Ellipsomitri (Nano-View, SE MG-1000; Ellipsometery).
<선택도><Selectivity>
선택도를 결정한 수식은 다음과 같다. The formula that determines the selectivity is as follows.
A: A: 실리콘질화막Silicon nitride film 에칭속도, B: Etching rate, B: 실리콘산화막Silicon oxide film 에칭속도. C: 선택도 Etching speed. C: selectivity
결과는 표 1과 같다.The results are shown in Table 1.
[표 1]TABLE 1
본 발명에 따르면 특정한 실리콘화합물과 옥심화합물을 함유한 조성물을 사용함으로써 실리콘 신화막에 대하여 식각 영향을 거의 끼치지 않으면서 실리콘 질화막만을 식각하는 것을 알 수 있으며, 이는 기존의 에칭액인 인산 대비 선택비를 2배 이상 증가시켜 실리콘질화막과 실리콘산화막의 혼재 사용시 공정상의 실리콘질화막의 제거를 보다 용이하게 하였으며, 불소화합물을 첨가하였을 경우 실리콘질화막의 식각속도를 2배 이상 증가시켜 공정시간을 단축시키는 이점이 있다. 도 1은 비교예 1의 식각액과 실시예 3의 식각액의 Batch에 따른 식각속도 변화를 나타난 그림이다. 도 1에서 인산은 Batch 수가 증가함에 따라 실리콘질화막의 식각속도가 감소하지만, 본 발명의 식각액 조성물은 Batch 수가 증가하여도 실리콘질화막의 식각속도가 변화하지 않는다.According to the present invention, it can be seen that by using a composition containing a specific silicon compound and an oxime compound, only the silicon nitride film is etched with little etching effect on the silicon mythium film. Increased by more than 2 times to make it easier to remove the silicon nitride film in the process when using a mixture of silicon nitride film and silicon oxide film, and the addition of fluorine compound has the advantage of shortening the process time by increasing the etching rate of the silicon nitride film by more than 2 times . 1 is a view showing a change in the etching rate according to the batch of the etchant of Comparative Example 1 and the etchant of Example 3. In FIG. 1, although the etching rate of the silicon nitride film decreases as the number of batches of phosphoric acid increases, the etching rate of the silicon nitride film does not change even if the number of batches of the etching solution composition of the present invention increases.
도 1은 비교예 1 식각액과 실시예 3 식각액의 Batch에 따른 식각속도 변화를 나타낸 그래프이다.1 is a graph showing the change in etching rate according to the batch of Comparative Example 1 etchant and Example 3 etchant.
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| KR20170066179A (en) * | 2015-12-04 | 2017-06-14 | 솔브레인 주식회사 | Composition for etching and manufacturing method of semiconductor device using the same |
| CN109563407A (en) * | 2018-11-13 | 2019-04-02 | 长江存储科技有限责任公司 | The additive of phosphoric acid etch agent |
| KR20210047140A (en) | 2019-10-21 | 2021-04-29 | 동우 화인켐 주식회사 | An etchant composition and a pattern formation method using the same |
| WO2023096266A1 (en) * | 2021-11-29 | 2023-06-01 | (주)후성 | Silicon nitride film etching composition and preparation method therefor |
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