KR102354378B1 - ETCHING COMPOSITION WITH HIGH SELECTIVITY TO TiN LAYER USING HYDROGEN PEROXIDE - Google Patents
ETCHING COMPOSITION WITH HIGH SELECTIVITY TO TiN LAYER USING HYDROGEN PEROXIDE Download PDFInfo
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- 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
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Abstract
본 발명은 반도체 공정에서 질화티탄막을 식각하여 제거하는 데 사용되는 것으로, 본 발명에 따른 질화티탄막을 선택적으로 식각하는 질화티탄막 식각용 조성물은 과산화수소, 질화티탄막 식각 가속제로 아민계 화합물, 텅스텐막 식각 억제제로 이미노 화합물을 포함한다.
본 발명에 따른 질화티탄막의 식각용 조성물은 과산화수소 안정성을 유지하여 고온 발열 및 급격한 조성 변화가 없고, 질화티탄막과 텅스텐막 중 텅스텐막 식각속도 대비 질화티탄막 식각속도가 높은 선택비로 식각한다.The present invention is used to etch and remove a titanium nitride film in a semiconductor process, and the composition for etching a titanium nitride film for selectively etching a titanium nitride film according to the present invention includes hydrogen peroxide, an amine-based compound as a titanium nitride film etch accelerator, and a tungsten film. Imino compounds are included as etch inhibitors.
The composition for etching a titanium nitride film according to the present invention maintains hydrogen peroxide stability, so there is no high temperature heat generation and rapid composition change, and the titanium nitride film etching rate is etched with a high selectivity ratio compared to the tungsten film etching rate among the titanium nitride film and the tungsten film.
Description
본 발명은 반도체 공정에서 질화티탄막을 식각하여 제거하는 데 사용되는 과산화수소를 이용한 질화티탄막의 식각용 조성물에 관한 것이다. 보다 상세하게는 과산화수소의 함량이 99% 이상 포함된 식각액 조성물로 텅스텐막 대비 질화티탄의 식각 속도가 선택적으로 높은 반도체 제조용 질화티탄막 식각을 위한 고선택비 식각용 조성물에 관한 것이다.The present invention relates to a composition for etching a titanium nitride film using hydrogen peroxide used to etch and remove the titanium nitride film in a semiconductor process. More specifically, it relates to a high-selectivity etching composition for etching a titanium nitride film for semiconductor manufacturing, which is an etchant composition containing 99% or more of hydrogen peroxide and has a selectively high etching rate of titanium nitride compared to a tungsten film.
일반적으로 티타늄(Ti), 질화티탄(TiN), 또는 티탄 합금은 액정 디스플레이, 반도체 디바이스, 프린트 배선 기판 등에 알루미늄(Al), 구리(Cu) 배선의 하지 또는 캡층으로 이용된다. 또한 반도체 디바이스에서는 배리어 메탈, 게이트 메탈로 사용되는 경우도 있다. 또한 텅스텐(W), 또는 텅스텐합금은 반도체 디바이스의 게이트 전극, 배선, 배리어층이나 컨텐트홀, 비어홀의 매립 또는 액정 디스플레이 등에 사용되고 있다. In general, titanium (Ti), titanium nitride (TiN), or a titanium alloy is used as a base or cap layer of aluminum (Al) and copper (Cu) wiring in liquid crystal displays, semiconductor devices, printed wiring boards, and the like. In addition, in semiconductor devices, it may be used as a barrier metal or a gate metal. In addition, tungsten (W) or tungsten alloy is used for a gate electrode of a semiconductor device, wiring, barrier layer, filling of a content hole, a via hole, or a liquid crystal display.
액정 디스플레이에 금속 배선을 형성하기 위해서는 일반적으로 금속막 위에 포토레지스트를 도포 및 노광 후 식각하여 선택적인 영역에 금속막을 남겨 금속 배선을 형성하고 있다. In order to form a metal wiring in a liquid crystal display, in general, a photoresist is coated on a metal film, exposed and then etched to leave a metal film in a selective area to form the metal wiring.
일반적으로 낮은 저항값을 가지고, 환경 문제가 없는 구리(Cu)가 금속 배선으로 각광받았으나, 실리콘 절연막과의 흡착성이 좋지 않아 단일막으로 사용하기 어렵다는 단점을 가지고 있다. 이러한 문제점을 해결하기 위해, 실리콘 절연막과 흡착성이 우수한 구리 합금막 (Cu Alloy), 티타늄 막, 티타늄 합금막 (Ti Alloy), 텅스텐 막, 텅스텐 합금막 (W Alloy) 등을 사용하고 있다.In general, copper (Cu), which has a low resistance value and has no environmental problems, has been in the spotlight as a metal wiring, but has a disadvantage in that it is difficult to use as a single layer due to poor adsorption with a silicon insulating layer. To solve this problem, a silicon insulating film and a copper alloy film (Cu Alloy), a titanium film, a titanium alloy film (Ti Alloy), a tungsten film, a tungsten alloy film (W Alloy), etc. having excellent adsorption properties are used.
또한 DRAM 시장에서 사용되는 질화티탄막 하드마스크(Hard Mask)는 약 20nm 이하의 DRAM 고 집적화된 것으로 종래의 막질 대비하여 경도가 더욱 높아지고 있는 추세이다. 따라서 종래의 질화티탄 및 텅스텐막의 선택비가 약 6:1의 비율을 가지고 있으므로, 상기의 이유로 선택비가 증가되어야 할 필요성이 있다. In addition, the titanium nitride film hard mask used in the DRAM market is highly integrated with DRAM of about 20 nm or less, and the hardness is increasing compared to the conventional film quality. Therefore, since the conventional titanium nitride and tungsten film have a selectivity ratio of about 6:1, there is a need to increase the selectivity for the above reasons.
한편 금속막을 식각하기 위해서 비용이 저렴하고, 성능이 우수한 과산화수소계 식각액을 사용하고 있다. 하지만 과산화수소계 식각액 내에 식각된 금속 이온들이 일정 농도 이상이 되면 과산화수소의 분해를 촉진시켜 물과 산소로 빠르게 분해되어 발열 및 급격한 조성변화가 일어날 수 있다는 문제가 있다. Meanwhile, in order to etch the metal film, a hydrogen peroxide-based etchant having low cost and excellent performance is used. However, when the metal ions etched in the hydrogen peroxide-based etchant exceed a certain concentration, the decomposition of hydrogen peroxide is accelerated to rapidly decompose into water and oxygen, thereby causing heat generation and rapid composition change.
대한민국 공개특허공보 제10-2015-0162229호에는 식각된 금속 이온들의 농도를 유지하기위해 메인 킬레이트제 및 서브 킬레이트제를 첨가하여 급격한 조성변화를 방지하기 위한 발명이 개시 되었다. 하지만 메인 킬레이트제 및 서브 킬레이트제를 첨가하여도 높은 과산화수소 안정성을 기대하기 어렵다는 문제가 있다.Korean Patent Laid-Open No. 10-2015-0162229 discloses an invention for preventing rapid compositional change by adding a main chelating agent and a sub-chelating agent to maintain the concentration of etched metal ions. However, there is a problem in that it is difficult to expect high hydrogen peroxide stability even when the main chelating agent and the sub-chelating agent are added.
또한, 대한민국 공개특허공보 제10-2010-0036364호는 식각액 조성물 내의 과산화수소 함량을 줄여 과산화수소 안정성을 유지하기 위한 발명이 개시 되었으나, 조성물 내에 과산화수소 함량을 줄인 경우, 질화티탄과 텅스텐의 식각 선택비가 충분히 구현되지 않는 문제점이 있다. In addition, Korean Patent Application Laid-Open No. 10-2010-0036364 discloses an invention for maintaining hydrogen peroxide stability by reducing the hydrogen peroxide content in the etchant composition, but when the hydrogen peroxide content is reduced in the composition, the etch selectivity of titanium nitride and tungsten is sufficiently implemented There is a problem that does not work.
대한민국 공개특허공보 제10-2013-0021321호에서는 종래의 막질에서 식각액 조성물 내의 과산화 수소 함량이 25 wt% 초과 증가 시 식각속도가 전체적으로 빨라져 공정 컨트롤의 어려움이 있다고 게시 하였으나, 질화티탄막 하드마스크(Hard Mask)가 약 20nm 이하의 DRAM 고 집적화됨에 따라 질화티탄막 하드 마스크의 경도가 높아짐에 따라 식각액 조성물 내의 과산화수소 함량이 더욱 증가되어야 할 필요가 있다.In Korean Patent Laid-Open Publication No. 10-2013-0021321, it was published that there was difficulty in process control due to the overall increase in the etch rate when the hydrogen peroxide content in the etchant composition increased by more than 25 wt% in the conventional film quality. Mask) of about 20 nm or less of DRAM, and as the hardness of the titanium nitride film hard mask increases, it is necessary to further increase the hydrogen peroxide content in the etchant composition.
상기 문제점을 해결하기 위하여, 본 발명은 식각액 조성물 중 과산화수소의 함량을 99% 이상으로 하고, 텅스텐막 대비 질화티탄막을 10:1 이상의 선택비로 식각하며, 과산화수소 안정성을 유지하여 고온 발열 및 급격한 조성 변화가 발생하지 않는 질화티탄막 식각을 위한 고선택비 식각용 조성물을 제공하고자 한다.In order to solve the above problems, the present invention sets the content of hydrogen peroxide in the etchant composition to 99% or more, etches the titanium nitride film with a selectivity ratio of 10:1 or more to the tungsten film, and maintains hydrogen peroxide stability to prevent high temperature exotherm and rapid composition change. An object of the present invention is to provide a high-selectivity etching composition for etching a titanium nitride film that does not occur.
상기의 목적을 달성하기 위하여 본 발명은 과산화수소, 질화티탄막 식각 가속제로 아민계 화합물, 텅스텐막 식각 억제제로 이미노 화합물을 포함하고, 텅스텐막 대비 질화티탄막을 선택적으로 식각하는 질화티탄막의 식각용 조성물을 제공한다.In order to achieve the above object, the present invention includes hydrogen peroxide, an amine compound as a titanium nitride film etch accelerator, and an imino compound as a tungsten film etch inhibitor, and a composition for etching a titanium nitride film that selectively etches a titanium nitride film compared to a tungsten film provides
또한, 본 발명은 총 중량 100 대비, 과산화수소 99.94~99.96 wt%, 아민계 화합물 0.01~0.05 wt%, 이미노 화합물 0.0075~0.05 wt%를 포함하는 질화티탄막의 식각용 조성물을 제공한다.In addition, the present invention provides a composition for etching a titanium nitride film comprising 99.94 to 99.96 wt% of hydrogen peroxide, 0.01 to 0.05 wt% of an amine compound, and 0.0075 to 0.05 wt% of an imino compound, based on a total weight of 100.
더욱 바람직하게는 본 발명은 총 중량 100 대비, 과산화수소 99.9425~99.95wt% 를 포함하는 질화티탄막의 식각용 조성물을 제공한다.More preferably, the present invention provides a composition for etching a titanium nitride film comprising 99.9425 to 99.95 wt% of hydrogen peroxide, based on a total weight of 100.
더욱 바람직하게는 상기 아민계 화합물은 총 중량 100 대비 0.03~0.05wt% 인 것을 특징으로 한다.More preferably, the amine-based compound is characterized in that 0.03 to 0.05 wt% based on the total weight of 100.
더욱 바람직하게는 상기 이미노 화합물은 총 중량 100 대비 0.0075~0.01wt% 인 것을 특징으로 한다.More preferably, the imino compound is characterized in that 0.0075 to 0.01wt% based on the total weight of 100.
또한, 본 발명은 텅스텐막 대비 질화티탄막 식각속도의 선택비가 10:1 이상인 질화티탄막의 식각용 조성물을 제공한다.In addition, the present invention provides a composition for etching a titanium nitride film in which the selectivity of the etch rate of the titanium nitride film to the tungsten film is 10:1 or more.
본 발명에 따른 질화티탄막의 식각용 조성물은 질화티탄막과 텅스텐막 중 텅스텐막 식각속도 대비 질화티탄막 식각속도가 10:1 이상의 선택비로 식각하는 효과가 있다.The composition for etching a titanium nitride film according to the present invention has an effect of etching the titanium nitride film and the tungsten film in a selectivity ratio of 10:1 or more compared to the etching rate of the tungsten film.
또한, 과산화수소 안정성을 유지하여 고온 발열 및 급격한 조성 변화가 없어 질화티탄막의 높은 선택비로 식각하는 효과가 있다. In addition, there is an effect of etching with a high selectivity of the titanium nitride film without high temperature heat generation and rapid composition change by maintaining hydrogen peroxide stability.
이하, 본 발명을 보다 구체적으로 설명한다. 본 발명의 실시예는 발명의 하나의 예시로서 제시되는 것으로, 이에 의해 발명의 권리 범위가 한정되는 것은 아니며, 발명의 권리 범위 내에서 구현예에 대한 다양한 변형이 가능함은 당업자에게 자명하다. 하기 실시예 및 비교예에 있어서 별도의 언급이 없으면 조성물의 성분비는 중량비로 계산된다. 본 발명의 실시예와 도면에 있어서 표현되는 식각속도는 식각용 조성물 평가 시간에 따라 비례하는 수치가 아니며, 제시된 평가조건 이외 환경에서 식각속도 및 선택비가 다르게 표현될 수 있다. Hereinafter, the present invention will be described in more detail. The embodiment of the present invention is presented as an example of the invention, whereby the scope of the invention is not limited, and it is apparent to those skilled in the art that various modifications to the embodiment are possible within the scope of the invention. In the following Examples and Comparative Examples, unless otherwise specified, the composition ratio is calculated by weight. The etching rate expressed in the examples and drawings of the present invention is not a numerical value proportional to the evaluation time of the etching composition, and the etching rate and selectivity may be expressed differently in environments other than the presented evaluation conditions.
본 발명에 따른 질화티탄막의 식각용 조성물은 과산화수소, 질화티탄막 식각 가속제로 아민계 화합물, 텅스텐막 식각 억제제로 이미노 화합물을 포함하고, 텅스텐막 대비 질화티탄막 식각속도의 선택비가 10:1 이상이다.The composition for etching a titanium nitride film according to the present invention contains hydrogen peroxide, an amine-based compound as a titanium nitride film etch accelerator, and an imino compound as a tungsten film etch inhibitor, and the selectivity of the etch rate of the titanium nitride film to the tungsten film is 10:1 or more to be.
상기 질화티탄막의 식각용 조성물은 전체 조성물 100 중량 기준으로 과산화수소 99.94~99.96 wt%, 아민계 화합물 0.01~0.05 wt%, 이미노 화합물 0.0075~0.01 wt%를 포함한다. The composition for etching the titanium nitride film includes 99.94 to 99.96 wt% of hydrogen peroxide, 0.01 to 0.05 wt% of an amine compound, and 0.0075 to 0.01 wt% of an imino compound based on 100 weight of the total composition.
과산화수소는 질화티탄막 식각을 위한 주 식각 성분으로, 텅스텐막을 산화시켜 전체적 선택비를 조절한다. 전체 조성물 총 중량 100 대비 과산화수소는 99.94 ~ 99.96 wt%로 포함된다. 과산화수소가 99.94 wt% 미만으로 포함되는 경우, 질화티탄막의 제거가 불충분하고, 전체적인 식각률 선택비가 저하될 수 있다. 한편, 과산화수소 함량이 99.96wt% 초과하여 포함되는 경우, 함량 증가에 따른 더 이상의 효과 상승을 기대하기 어렵다. 더욱바람직하게는 상기 과산화수소는 총 중량 100 대비, 99.9425~99.95wt%로 포함된다. Hydrogen peroxide is a main etching component for etching the titanium nitride film, and oxidizes the tungsten film to control the overall selectivity. Hydrogen peroxide is contained in an amount of 99.94 to 99.96 wt% based on 100 of the total weight of the composition. When hydrogen peroxide is included in an amount of less than 99.94 wt%, the removal of the titanium nitride film may be insufficient, and the overall etch rate selectivity may be reduced. On the other hand, when the hydrogen peroxide content is included in excess of 99.96 wt%, it is difficult to expect any further increase in the effect according to the content increase. More preferably, the hydrogen peroxide is contained in an amount of 99.9425 to 99.95 wt%, based on the total weight of 100.
상기 아민계 화합물은 질화티탄막 식각 가속제로서 질화티탄막의 식각률을 증가시켜 반도체의 집적화로 인해 경도가 높아진 질화티탄막의 식각에 효과적이다. 또한 장시간 에칭에 사용할 때 질화티탄막 식각 속도 및 텅스텐막 식각 속도를 유지시켜 선택비를 유지시켜 준다.The amine-based compound is a titanium nitride film etch accelerator, which increases the etch rate of the titanium nitride film, and thus is effective in etching the titanium nitride film having increased hardness due to semiconductor integration. In addition, when used for long-term etching, the selectivity is maintained by maintaining the etching rate of the titanium nitride film and the etching rate of the tungsten film.
상기 아민계 화합물은 0.01~0.05 wt%로 포함된다. 상기 아민계 화합물을 0.01 wt% 미만으로 첨가하는 경우 질화티탄막의 식각률이 저하되어 선택비가 낮아지고, 아민계 화합물을 0.07 중량%를 초과하여 첨가하는 경우, 질화티탄막 식각 가속제로서의 역할이 미미하여 질화티탄막의 삭각률이 감소한다. 따라서 선택비가 떨어지게 된다. 더욱 바람직하게는 아민계 화합물은 0.03~0.05중량%로 포함된다.The amine-based compound is included in an amount of 0.01 to 0.05 wt%. When the amine-based compound is added in an amount of less than 0.01 wt%, the etch rate of the titanium nitride film is lowered and the selectivity is lowered. The reduction rate of the titanium film decreases. Therefore, the selection cost decreases. More preferably, the amine-based compound is included in an amount of 0.03 to 0.05% by weight.
상기 아민계 화합물은 테트라에틸렌펜타아민 (Tetraetylenepentamine), 다이프로필아민 (Dipropylamine), 에틸디에탄올아민(N-Ethyldiethanolamine), 사이클로헥실아민 (Cyclohexylamine), 모노에탄올아민 (Monoethanolamine), 디사이클로헥실아민 (Dicyclohexylamine), 디벤질아민 (Dibenzylamine), 트리프로필아민 (Tripropylamine), 2-에틸헥실아민 (2-Ethyl-1-hexylamine), 디에틸렌트리아민 (Diethylenetriamine), 트리에틸렌테트라아민 (Triethylenetetramine), 트리부틸아민 (Tributylamine) 테트라부틸아민(Tert-butylamine), 1,4-butanediamine, 4,4-dimethylcyclohexanamine, 에틸아민 (Ethylamine), 아닐린 (Aniline), 톨루이딘(Toluidine), 이소프로필아민 (Isopropylamine), 어니시딘(Anisidine), 펜티딘 (Phenetidine), butane-1,4-diamine, Naphthalene-1,8-diamine, 7-(Aminomethyl)dibenzofuran-2,3-bis(ethylamine)으로부터 1 이상 선택된다. The amine-based compound is tetraethylenepentamine (Tetraetylenepentamine), dipropylamine (Dipropylamine), ethyldiethanolamine (N-Ethyldiethanolamine), cyclohexylamine (Cyclohexylamine), monoethanolamine (Monoethanolamine), dicyclohexylamine (Dicyclohexylamine) ), dibenzylamine, tripropylamine, 2-ethylhexylamine (2-Ethyl-1-hexylamine), diethylenetriamine, triethylenetetramine, tributylamine (Tributylamine) Tetrabutylamine, 1,4-butanediamine, 4,4-dimethylcyclohexanamine, Ethylamine, Aniline, Toluidine, Isopropylamine, Anisidine (Anisidine), pentidine (Phenetidine), butane-1,4-diamine, Naphthalene-1,8-diamine, and at least one selected from 7-(Aminomethyl)dibenzofuran-2,3-bis(ethylamine).
상기 이미노 화합물은 텅스텐막 식각 억제제로 조성물 총 중량 100 대비, 0.007 ~ 0.01 wt%로 함유된다. 이미노 화합물을 0.005 wt% 미만으로 첨가하는 경우, 텅스텐막 식각 억제 효율이 떨어져 텅스텐막의 식각률이 상승하고 그로 인해 높은 식각 선택비를 얻을 수 없으며, 이미노 화합물을 0.01 wt%를 초과하여 첨가하는 경우, 고온의 발열반응이 발생하고 함량 증가에 따른 효과 상승을 기대하기 어렵다. 더욱 바람직하게는 상기 이미노 화합물은 조성물 총 중량 100 대비 0.0075 ~ 0.01 wt%로 첨가한다.The imino compound is a tungsten film etch inhibitor and is contained in an amount of 0.007 to 0.01 wt%, based on the total weight of 100 of the composition. When the imino compound is added in an amount of less than 0.005 wt%, the tungsten film etching inhibition efficiency is lowered, and the etch rate of the tungsten film is increased, and thus a high etch selectivity cannot be obtained. When the imino compound is added in excess of 0.01 wt% , an exothermic reaction at high temperature occurs, and it is difficult to expect an increase in the effect as the content increases. More preferably, the imino compound is added in an amount of 0.0075 to 0.01 wt% based on 100 of the total weight of the composition.
상기 이미노 화합물은 프롤린(Proline), 아지리딘(aziridine), poly[imino(1-chloro-2-oxoethylene)(4-nitro-1,3-phenylene)(3-bromopropane-1,3-diyl)], poly[(methylimino)methyleneimino-1,3-phenylene], poly[imino(1-oxoethylene)silanediylpropane-1,3-diyl], poly[oxy(1,1-dichloroethylene)imino(1-oxoethylene)], poly[imino(x-methyl-1,3-phenylene)iminomalonyl], poly[oxyhexane-1,6-diyloxycarbonylimino(methylphenylene)iminocarbonyl], poly(oxyiminomethylenehydrazine-1,2-diylmethylene), poly{imino[1-oxo-2-(phenylsulfanyl)ethylene]}, Polyethylenimine, 1-Hexanimine, 4-imino2,5-cyclohexadien-1-one, 1,3-dihydro-3[(5-mercapto-1,3,4-thiadiazol-2-yl)imino]-2H-indol-2-one, Hexafluoroacetoneimine, 2,2-Iminodi-4-quinolineacetic acid, 4,4-Iminodibenzoic acid, 3,3-(2,6-pyridinediyldiimino)dipropionic acid, 3,3,3-Nitrilotripropionic acid, poly imino 1,3 phenylene, o-iminophenolate 으로부터 1 이상 선택된다. The imino compound is proline (Proline), aziridine (aziridine), poly[imino (1-chloro-2-oxoethylene) (4-nitro-1,3-phenylene) (3-bromopropane-1,3-diyl) ], poly[(methylimino)methyleneimino-1,3-phenylene], poly[imino(1-oxoethylene)silanediylpropane-1,3-diyl], poly[oxy(1,1-dichloroethylene)imino(1-oxoethylene)] , poly[imino(x-methyl-1,3-phenylene)iminomalonyl], poly[oxyhexane-1,6-diyloxycarbonylimino(methylphenylene)iminocarbonyl], poly(oxyiminomethylenehydrazine-1,2-diylmethylene), poly{imino[1- oxo-2-(phenylsulfanyl)ethylene]}, Polyethylenimine, 1-Hexanimine, 4-imino2,5-cyclohexadien-1-one, 1,3-dihydro-3[(5-mercapto-1,3,4-thiadiazol- 2-yl)imino]-2H-indol-2-one, Hexafluoroacetoneimine, 2,2-Iminodi-4-quinolineacetic acid, 4,4-Iminodibenzoic acid, 3,3-(2,6-pyridinediyldiimino)dipropionic acid, 3 One or more selected from ,3,3-Nitrilotripropionic acid, poly imino 1,3 phenylene, and o-iminophenolate.
상기 질화티탄막의 식각용 조성물은 과산화수소의 함량이 99% 이상 함유되고 텅스텐막 대비하여 질화티탄막을 선택적으로 식각한다. 본 발명에 따른 질화티탄막의 식각용 조성물은 텅스텐막 식각속도 대비 질화티탄막 식각속도의 선택비가 10:1 이상이다. The composition for etching the titanium nitride film contains 99% or more of hydrogen peroxide and selectively etches the titanium nitride film compared to the tungsten film. In the composition for etching a titanium nitride film according to the present invention, the selectivity of the etching rate of the titanium nitride film to the etching rate of the tungsten film is 10:1 or more.
식각용 조성물의 제조Preparation of etching composition
본 발명에 따른 질화티탄막의 식각용 조성물은 과산화수소, 질화티탄막 식각 가속제로 아민계 화합물, 텅스텐막 식각 억제제로 이미노 화합물을 포함하고, 전체 조성물 100 중량 대비, 과산화수소 99.94~99.96 wt%, 아민계 화합물 0.01~0.05 wt%, 이미노 화합물 0.0075~0.01 wt%를 포함하여 제조한다. The composition for etching a titanium nitride film according to the present invention contains hydrogen peroxide, an amine compound as a titanium nitride film etching accelerator, and an imino compound as a tungsten film etching inhibitor, and 99.94 to 99.96 wt% of hydrogen peroxide, based on 100 weight of the total composition, amine-based compound It is prepared including 0.01 to 0.05 wt% of the compound, and 0.0075 to 0.01 wt% of the imino compound.
비교예 1Comparative Example 1
과산화수소 100 wt% 로 비교예 1로 하고, 비교예 1을 사용하여 식각 속도를 측정하였다. 100 wt% of hydrogen peroxide was used as Comparative Example 1, and the etching rate was measured using Comparative Example 1.
비교예 2Comparative Example 2
과산화수소 99.95 wt%, 아민계 화합물로 아닐린 (Aniline) 0.05wt%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 비교예 2에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.95 wt% of hydrogen peroxide and 0.05 wt% of aniline as an amine compound was prepared. And the etching rate was measured using the composition according to Comparative Example 2.
비교예 3Comparative Example 3
과산화수소 99.99wt%, 이미노 화합물로 프롤린(Proline) 0.01중량%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 비교예 3에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.99 wt% of hydrogen peroxide and 0.01 wt% of proline as an imino compound was prepared. And the etching rate was measured using the composition according to Comparative Example 3.
비교예4Comparative Example 4
과산화수소 99.95 wt%, 아민계 화합물로 아닐린 (Aniline) 0.05wt%, 텅스텐막 식각 억제제로 대표되는 이미노 화합물로 프롤린(Proline) 0.05 wt%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 비교예 4에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.95 wt% of hydrogen peroxide, 0.05 wt% of aniline as an amine compound, and 0.05 wt% of proline as an imino compound represented by a tungsten film etching inhibitor was prepared. And the etching rate was measured using the composition according to Comparative Example 4.
실시예1Example 1
과산화수소 99.9425 wt%, 질화티탄막 식각 가속제로 아민계 화합물로 아닐린 (Aniline) 0.05wt%, 텅스텐막 식각 억제제로 이미노 화합물로 프롤린(Proline) 0.0075wt%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 실시예 1에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.9425 wt% of hydrogen peroxide, 0.05 wt% of aniline as an amine-based compound as a titanium nitride film etching accelerator and 0.0075 wt% of proline as an imino compound as an tungsten film etching inhibitor was prepared. And the etching rate was measured using the composition according to Example 1.
실시예2Example 2
과산화수소 99.94 wt%, 아민계 화합물로 아닐린 (Aniline) 0.05wt%, 이미노 화합물로 프롤린(Proline) 0.01 wt%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 실시예 2에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.94 wt% of hydrogen peroxide, 0.05 wt% of aniline as an amine compound, and 0.01 wt% of proline as an imino compound was prepared. And the etching rate was measured using the composition according to Example 2.
실시예3Example 3
과산화수소 99.96 wt%, 아민계 화합물로 아닐린 (Aniline) 0.03wt%, 이미노 화합물로 프롤린(Proline) 0.01 wt%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 실시예 3에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.96 wt% of hydrogen peroxide, 0.03 wt% of aniline as an amine compound, and 0.01 wt% of proline as an imino compound was prepared. And the etching rate was measured using the composition according to Example 3.
실시예4Example 4
과산화수소 99.95 wt%, 질화티탄막 식각 가속제로 대표되는 아민계 화합아민계 화합물로 아닐린 (Aniline) 0.04wt%, 이미노 화합물로 프롤린(Proline) 0.01 wt%의 조성을 가지는 식각용 조성물을 제조하였다. 그리고 실시예 4에 따른 조성물을 사용하여 식각 속도를 측정하였다. An etching composition having a composition of 99.95 wt% of hydrogen peroxide, 0.04 wt% of aniline as an amine compound represented by a titanium nitride film etching accelerator, and 0.01 wt% of proline as an imino compound was prepared. And the etching rate was measured using the composition according to Example 4.
식각용 조성물의 식각 속도 및 선택비 구현 평가Evaluation of implementation of etching rate and selectivity of etching composition
본 발명에 따른 각 실시예들은 과산화수소, 질화티탄막 식각 가속제로 대표되는 아민계 화합물, 텅스텐막 식각 억제제로 대표되는 이미노 화합물을 포함한 식각용 조성물을 사용하여 식각속도 및 선택비 구현 여부를 평가한다. Each embodiment according to the present invention evaluates whether the etching rate and selectivity are implemented using an etching composition including hydrogen peroxide, an amine compound represented by a titanium nitride film etching accelerator, and an imino compound represented by a tungsten film etching inhibitor. .
상기 비교예와 실시예에 따른 각각의 조성물을 평가 식각용 조성물로 하고, 투입양은 300g으로 투입하고, 75℃도까지 온도를 높인 후 질화티탄막 및 텅스텐막을 Dipping 하여 식각속도 및 선택비 구현 여부를 평가하였다. 식각속도 측정을 위한 질화티탄막 및 텅스텐막은 2,000Å 두께를 가지는 막으로 평가를 위해 가로 1㎝, 세로 3 ㎝의 시편으로 제조하여 식각 전후 두께를 측정하였다. 식각평가 시간은 질화티탄막 5분, 텅스텐막 10분으로하고 평가 전후 두께를 측정하였다. 질화티탄막 및 텅스텐막의 식각 속도는 분당 식각 속도로 계산되며, 선택비는 텅스텐막 식각속도 대비 질화티탄막 식각속도의 비로 계산하였다. Each composition according to the Comparative Examples and Examples was used as an etching composition for evaluation, and the amount was added at 300 g, and the temperature was raised to 75 ° C. evaluated. A titanium nitride film and a tungsten film for measuring the etch rate were prepared with specimens having a width of 1 cm and a length of 3 cm for evaluation as films having a thickness of 2,000 Å, and thicknesses before and after etching were measured. The etching evaluation time was 5 minutes for the titanium nitride film and 10 minutes for the tungsten film, and the thickness before and after the evaluation was measured. The etching rates of the titanium nitride film and the tungsten film were calculated as the etching rate per minute, and the selectivity was calculated as the ratio of the etching rate of the titanium nitride film to the etching rate of the tungsten film.
[A: 질화티탄막의 식각속도, B: 텅스텐막의 식각속도, C: 선택비][A: etching rate of titanium nitride film, B: etching rate of tungsten film, C: selectivity]
하기 실시예 및 비교예에 있어서 식각속도 평가는 평판 질화티탄 및 텅스텐막을 식각평가 하여 식각률을 계산한 결과로 요구되는 질화티탄막 및 텅스텐막의 식각속도에 부합 여부를 판단하여, O : Excellent, △ : Good, X : Bad로 수치를 부여하였다.In the following Examples and Comparative Examples, the etching rate evaluation is performed by evaluating the etching rate of the flat titanium nitride film and the tungsten film, and determining whether the etching rate of the titanium nitride film and the tungsten film corresponds to the required etching rate, O: Excellent, △: Good, X: A value was assigned to Bad.
표 1은 본 발명에 따른 실시예들 및 비교예의 질화티탄막, 텅스텐막의 식각속도와 수치 그리고 선택비를 나타낸 것이다. Table 1 shows the etching rate, numerical value, and selectivity of the titanium nitride film and the tungsten film of Examples and Comparative Examples according to the present invention.
식각률 수치 및 선택비 평가결과Etching rate value and selection ratio evaluation result
비교예 1을 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 53.32 Å/min, 텅스텐막 10분 Dipping에서 9.74 Å/min으로 질화티탄막 식각 속도의 불량하고, 텅스텐막의 식각 속도 높아 선택비가 낮아졌다.As a result of measuring the etching rate using Comparative Example 1, the etch rate was 53.32 Å/min at 5 minutes dipping of the titanium nitride film and 9.74 Å/min at 10 minutes of dipping of the tungsten film. .
비교예 2를 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 64.10 Å/min, 텅스텐막 10분 Dipping에서 10.20Å/min으로 비교예1 대비 질화티탄막 식각 속도 증가하여 개선되었으나, 텅스텐막 식각 속도 동등 수준으로 유지되어 선택비가 약 6으로 낮게 측정되었다.As a result of measuring the etch rate using Comparative Example 2, the etch rate of the titanium nitride film was increased to 64.10 Å/min at 5 minutes dipping of the titanium nitride film and 10.20 Å/min at 10 minutes of dipping of the tungsten film. The rate was maintained at the same level, and the selectivity was measured as low as about 6.
비교예 3에 따른 조성물을 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 46.42 Å/min, 텅스텐막 10분 Dipping에서 1.69 Å/min으로 비교예1 대비하여 질화티탄막과 텅스텐막 모두 식각 속도가 현저하게 줄어들어 선택비가 약 27로 급격히 상승하였다. 또한 비교예1, 비교예2 대비하여 텅스텐막 식각 속도 현저히 줄어들어 선택비 급격히 증가하였으나, 질화티탄막 식각 속도 또한 줄어들었다. As a result of measuring the etching rate using the composition according to Comparative Example 3, the etch rate of both the titanium nitride film and the tungsten film compared to Comparative Example 1 was 46.42 Å/min at 5 minutes dipping of the titanium nitride film and 1.69 Å/min at 10 minutes of dipping of the tungsten film. was significantly reduced, and the selectivity increased sharply to about 27. In addition, compared to Comparative Examples 1 and 2, the etching rate of the tungsten film was significantly reduced, and the selectivity was sharply increased, but the etching rate of the titanium nitride film was also reduced.
비교예 4에 따른 조성물을 사용하여 식각 속도 측정 결과 고온 발열 발생하여 식각 속도 측정이 불가하였다.As a result of measuring the etch rate using the composition according to Comparative Example 4, high-temperature exotherm occurred, so that the etch rate could not be measured.
실시예 1에 따른 조성물을 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 60.24 Å/min, 텅스텐막 10분 Dipping에서 4.14 Å/min으로 비교예1, 비교예3 대비하여 질화티탄막의 식각 속도 증가한 결과를 보이고, 비교예1, 비교예2 대비하여 텅스텐막의 식각 속도가 현저히 줄어들었다. 평가 결과 텅스텐막 대비 질화티탄막의 식각 속도 선택비는 약 14로 비교예1, 비교예2 대비 높으며 텅스텐막의 식각 속도 개선됨을 확인하였고, 질화티탄막의 식각 속도 또한 증가하여 약 14의 선택비를 구현하였다. As a result of measuring the etching rate using the composition according to Example 1, the etch rate of the titanium nitride film was 60.24 Å/min in 5 minutes dipping of the titanium nitride film, and 4.14 Å/min in 10 minutes of dipping of the tungsten film, compared to Comparative Examples 1 and 3, the etching rate of the titanium nitride film. The result was increased, and the etching rate of the tungsten film was significantly reduced compared to Comparative Examples 1 and 2. As a result of the evaluation, the etch rate selectivity of the titanium nitride film to the tungsten film was about 14, which was higher than Comparative Examples 1 and 2, and it was confirmed that the etching rate of the tungsten film was improved. .
실시예2에 따른 조성물을 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 62.60 Å/min, 텅스텐막 10분 Dipping에서 3.43 Å/min으로 비교예1, 비교예2 대비하여 특히 텅스텐막의 식각 속도 현저히 감소하고, 비교예 3 대비하여 질화티탄막의 식각 속도 증가하여 약 18의 높은 선택비가 구현되었다. As a result of measuring the etching rate using the composition according to Example 2, the etching rate of the tungsten film was 62.60 Å/min at 5 minutes dipping of the titanium nitride film and 3.43 Å/min at 10 minutes of dipping of the tungsten film, especially compared to Comparative Examples 1 and 2 Remarkably decreased, compared to Comparative Example 3, the etching rate of the titanium nitride film increased, and a high selectivity of about 18 was realized.
실시예 3에 따른 조성물을 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 50.32 Å/min, 텅스텐막 10분 Dipping에서 3.60 Å/min으로 비교예1, 비교예2 대비하여 질화티탄막 식각속도 동등 수준이고, 비교예3 대비 텅스텐막 식각 속도 동등 수준으로 측정되어 약 13의 높은 선택비 구현됨을 확인하였다. As a result of measuring the etching rate using the composition according to Example 3, the titanium nitride film etching rate was 50.32 Å/min at 5 minutes dipping and 3.60 Å/min at the tungsten film 10 minute dipping, compared to Comparative Examples 1 and 2, respectively. The tungsten film etch rate was equivalent to that of Comparative Example 3, and it was confirmed that a high selectivity of about 13 was realized.
실시예 4에 따른 조성물을 사용하여 식각 속도 측정 결과 질화티탄막 5분 Dipping에서 55.70 Å/min, 텅스텐막 10분 Dipping에서 3.41 Å/min으로 비교예3 대비하여 질화티탄막 식각 속도 증가하였고, 비교예1, 비교예2 텅스텐 식각 속도 감소하여 선택비 약 16의 높은 수준 구현됨을 확인하였다. As a result of measuring the etching rate using the composition according to Example 4, the etch rate of the titanium nitride film was increased to 55.70 Å/min at 5 minutes dipping of the titanium nitride film and 3.41 Å/min at 3.41 Å/min at 10 minutes of dipping of the tungsten film. Example 1, Comparative Example 2 It was confirmed that a high level of selectivity of about 16 was achieved by decreasing the tungsten etching rate.
본 발명에 따른 과산화수소, 아민계 화합물, 이미노 화합물을 각 함량비로 제조한 질화티탄막의 식각용 조성물은 비교예1, 비교예2 대비하여 낮은 수준의 텡스텐막 식각 속도를 구현할 수 있다. 또한 비교예3 과 대비하여 질화티탄막 식각 속도를 상승시켜 높은 선택비를 구현할 수 있다. The composition for etching a titanium nitride film prepared in each content ratio of hydrogen peroxide, an amine-based compound, and an imino compound according to the present invention can implement a low level of tungsten film etching rate compared to Comparative Examples 1 and 2. In addition, a high selectivity can be realized by increasing the etching rate of the titanium nitride film as compared with Comparative Example 3.
그리고 실시예1, 실시예2, 실시예3 과 실시예4에서 보여지는 바와 같이, 아민계 화합물의 적정량의 첨가로 질화티탄막의 식각 속도가 증가되고, 이미노 화합물의 적정량의 첨가로 텅스텐막의 식각 속도가 감소되어 선택비의 증가로 이어지는 것을 확인할 수 있다. 이처럼 각 실시예에서 이미노 화합물의 함량에 따른 텅스텐막 식각속도와 아민계 화합물의 함량에 따른 질화티탄막 식각속도가 보여주는 바와 같이, 이미노 화합물과 아민계 화합물의 함량에 따라 질화티탄막의 식각속도는 증가하고, 텅스텐막의 식각속도는 줄어들어 높은 질화티탄막 식각속도의 높은 선택비를 얻을 수 있다. And as shown in Examples 1, 2, 3 and 4, the etching rate of the titanium nitride film is increased by the addition of an appropriate amount of the amine-based compound, and the etching of the tungsten film is etched by the addition of an appropriate amount of the imino compound. It can be seen that the speed is decreased, leading to an increase in the selectivity ratio. As shown in the tungsten film etching rate according to the content of the imino compound and the etching rate of the titanium nitride film according to the content of the amine compound in each Example, the etching rate of the titanium nitride film according to the content of the imino compound and the amine compound. increases, and the etching rate of the tungsten film decreases, so that a high selectivity of the etching rate of the titanium nitride film can be obtained.
본 발명에 따른 질화티탄막의 식각용 조성물은 반도체 공정에서 질화티탄막을 식각하여 제거하는 데 사용되며, 텅스텐막 식각속도 대비 질화티탄막 식각속도가 높은 선택비로 식각하고, 과산화수소 안정성을 유지하여, 고온 발열 및 급격한 조성 변화가 없어 질화티탄막의 선택적 식각이 필요한 공정에서 효과적으로 적용될 수 있다. The composition for etching a titanium nitride film according to the present invention is used to etch and remove a titanium nitride film in a semiconductor process, and etches with a high selectivity ratio of the etch rate of the titanium nitride film compared to the etch rate of the tungsten film, and maintains hydrogen peroxide stability and heats up at high temperature And since there is no rapid composition change, it can be effectively applied to a process requiring selective etching of a titanium nitride film.
Claims (8)
총 중량 100 대비, 과산화수소 99.94~99.96 wt%, 아민계 화합물 0.01~0.05 wt%, 이미노 화합물 0.0075~0.05 wt%를 포함하는 것을 특징으로 하는 질화티탄막의 식각용 조성물. 질화티탄막의 식각용 조성물.
It selectively etches the titanium nitride film compared to the tungsten film, including hydrogen peroxide, an amine compound as an etch accelerator for the titanium nitride film, and an imino compound as a tungsten film etch inhibitor,
A composition for etching a titanium nitride film, comprising 99.94 to 99.96 wt% of hydrogen peroxide, 0.01 to 0.05 wt% of an amine compound, and 0.0075 to 0.05 wt% of an imino compound, based on a total weight of 100. A composition for etching a titanium nitride film.
상기 과산화수소는 총 중량 100 대비 99.9425~99.95wt%를 포함하는 것을 특징으로 하는 질화티탄막의 식각용 조성물.
2. The method of claim 1
The composition for etching a titanium nitride film, characterized in that the hydrogen peroxide comprises 99.9425 to 99.95 wt% based on the total weight of 100.
상기 아민계 화합물은
테트라에틸렌펜타아민 (Tetraetylenepentamine), 다이프로필아민 (Dipropylamine), 에틸디에탄올아민(N-Ethyldiethanolamine), 사이클로헥실아민 (Cyclohexylamine), 모노에탄올아민 (Monoethanolamine), 디사이클로헥실아민 (Dicyclohexylamine), 디벤질아민 (Dibenzylamine), 트리프로필아민 (Tripropylamine), 2-에틸헥실아민 (2-Ethyl-1-hexylamine), 디에틸렌트리아민 (Diethylenetriamine), 트리에틸렌테트라아민 (Triethylenetetramine), 트리부틸아민 (Tributylamine) 테트라부틸아민(Tert-butylamine), 1,4-butanediamine, 4,4-dimethylcyclohexanamine, 에틸아민 (Ethylamine), 아닐린 (Aniline), 톨루이딘(Toluidine), 이소프로필아민 (Isopropylamine), 어니시딘(Anisidine), 펜티딘 (Phenetidine), butane-1,4-diamine, Naphthalene-1,8-diamine, 7-(Aminomethyl)dibenzofuran-2,3-bis(ethylamine)으로부터 1 이상 선택되는 것을 특징으로 하는 질화티탄막의 식각용 조성물.
The method of claim 1,
The amine compound is
Tetraetylenepentamine, Dipropylamine, N-Ethyldiethanolamine, Cyclohexylamine, Monoethanolamine, Dicyclohexylamine, Dibenzylamine (Dibenzylamine), tripropylamine (Tripropylamine), 2-ethylhexylamine (2-Ethyl-1-hexylamine), diethylenetriamine (Diethylenetriamine), triethylenetetramine (Triethylenetetramine), tributylamine (Tributylamine) tetrabutyl Amine (Tert-butylamine), 1,4-butanediamine, 4,4-dimethylcyclohexanamine, ethylamine (Ethylamine), aniline (Aniline), toluidine (Toluidine), isopropylamine (Isopropylamine), anisidine (Anisidine), penty For etching of titanium nitride film, characterized in that at least one selected from phenetidine, butane-1,4-diamine, Naphthalene-1,8-diamine, and 7-(Aminomethyl)dibenzofuran-2,3-bis(ethylamine) composition.
상기 이미노 화합물은
프롤린(Proline), 아지리딘(aziridine), poly[imino(1-chloro-2-oxoethylene)(4-nitro-1,3-phenylene)(3-bromopropane-1,3-diyl)], poly[(methylimino)methyleneimino-1,3-phenylene], poly[imino(1-oxoethylene)silanediylpropane-1,3-diyl], poly[oxy(1,1-dichloroethylene)imino(1-oxoethylene)], poly[imino(x-methyl-1,3-phenylene)iminomalonyl], poly[oxyhexane-1,6-diyloxycarbonylimino(methylphenylene)iminocarbonyl], poly(oxyiminomethylenehydrazine-1,2-diylmethylene), poly{imino[1-oxo-2-(phenylsulfanyl)ethylene]}, Polyethylenimine, 1-Hexanimine, 4-imino2,5-cyclohexadien-1-one, 1,3-dihydro-3[(5-mercapto-1,3,4-thiadiazol-2-yl)imino]-2H-indol-2-one, Hexafluoroacetoneimine, 2,2-Iminodi-4-quinolineacetic acid, 4,4-Iminodibenzoic acid, 3,3-(2,6-pyridinediyldiimino)dipropionic acid, 3,3,3-Nitrilotripropionic acid, poly imino 1,3 phenylene, o-iminophenolate 으로부터 1 이상 선택되는 것을 특징으로 하는 질화티탄막의 식각용 조성물.
2. The method of claim 1
The imino compound is
Proline, aziridine, poly[imino(1-chloro-2-oxoethylene)(4-nitro-1,3-phenylene)(3-bromopropane-1,3-diyl)], poly[( methylimino)methyleneimino-1,3-phenylene], poly[imino(1-oxoethylene)silanediylpropane-1,3-diyl], poly[oxy(1,1-dichloroethylene)imino(1-oxoethylene)], poly[imino( x-methyl-1,3-phenylene)iminomalonyl], poly[oxyhexane-1,6-diyloxycarbonylimino(methylphenylene)iminocarbonyl], poly(oxyiminomethylenehydrazine-1,2-diylmethylene), poly{imino[1-oxo-2-( phenylsulfanyl)ethylene]}, Polyethylenimine, 1-Hexanimine, 4-imino2,5-cyclohexadien-1-one, 1,3-dihydro-3[(5-mercapto-1,3,4-thiadiazol-2-yl)imino ]-2H-indol-2-one, Hexafluoroacetoneimine, 2,2-Iminodi-4-quinolineacetic acid, 4,4-Iminodibenzoic acid, 3,3-(2,6-pyridinediyldiimino)dipropionic acid, 3,3,3- Nitrilotripropionic acid, poly imino 1,3 phenylene, o-iminophenolate composition for etching a titanium nitride film, characterized in that at least one selected from the group consisting of.
상기 아민계 화합물은 총 중량 100 대비 0.03~0.05wt% 인 것을 특징으로 하는 질화티탄막 식각용 조성물.
The method of claim 1,
The composition for etching a titanium nitride film, characterized in that the amine-based compound is 0.03 to 0.05wt% based on the total weight of 100.
상기 이미노 화합물은 총 중량 100 대비 0.0075~0.01wt% 인 것을 특징으로 하는 질화티탄막 식각용 조성물.
The method of claim 1,
The imino compound is a titanium nitride film etching composition, characterized in that 0.0075 ~ 0.01wt% based on the total weight of 100.
텅스텐막 대비 질화티탄막 식각속도의 선택비가 10:1 이상인 것을 특징으로 하는 질화티탄막의 식각용 조성물.The method of claim 1,
A composition for etching a titanium nitride film, characterized in that the selectivity ratio of the etching rate of the titanium nitride film to the tungsten film is 10:1 or more.
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| EP2798669B1 (en) * | 2011-12-28 | 2021-03-31 | Entegris, Inc. | Compositions and methods for selectively etching titanium nitride |
| KR20170045865A (en) * | 2015-10-20 | 2017-04-28 | 동우 화인켐 주식회사 | Non-aqueous etching composition |
| KR102415954B1 (en) * | 2016-01-12 | 2022-07-01 | 동우 화인켐 주식회사 | ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME |
| KR102740456B1 (en) * | 2016-11-29 | 2024-12-06 | 삼성전자주식회사 | Etching composition and method for fabricating semiconductor device by using the same |
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2019
- 2019-08-27 KR KR1020190105421A patent/KR102354378B1/en active Active
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