KR20190094366A - 기판 상에 구조물을 형성하는 방법 - Google Patents

기판 상에 구조물을 형성하는 방법 Download PDF

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KR20190094366A
KR20190094366A KR1020197016743A KR20197016743A KR20190094366A KR 20190094366 A KR20190094366 A KR 20190094366A KR 1020197016743 A KR1020197016743 A KR 1020197016743A KR 20197016743 A KR20197016743 A KR 20197016743A KR 20190094366 A KR20190094366 A KR 20190094366A
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precursor
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hardmask material
hardmask
reaction chamber
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베르너 크네펜
얀 빌렘 메스
베르트 용블루트
크지슈토프 카밀 카헬
디터 피에뢰
루스트 다피트 쿠르트 데
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에이에스엠 아이피 홀딩 비.브이.
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Abstract

기판 상에 층을 형성하는 방법이 기판에 하드마스크 재료를 제공함으로써 제공된다. N 회의 침투 사이클 동안에 하드마스크 재료가 침투 재료로 침투되는 바, 각각의 침투 사이클은 a) 반응 챔버에서 기판 상의 침투 재료에 제1 기간(T1) 동안 제1 전구체를 제공하는 단계, b) 제2 기간(T2) 동안 제1 전구체의 일부분을 제거하는 단계, 그리고 c) 제3 기간(T3) 동안 기판 상의 하드마스크 재료에 제2 전구체를 제공해서, 상기 제1 전구체 및 상기 제2 전구체가 서로 반응해서 상기 침투 재료를 형성하는 단계를 포함할 수 있다.

Description

기판 상에 구조물을 형성하는 방법
본 개시는 일반적으로 전자 소자 제조용 방법 및 시스템에 관한 것이다. 보다 구체적으로, 본 개시는 기판 상에 구조물을 형성하는 방법에 관한 것이다.
반도체 소자의 크기가 점점 더 작아지는 추세로 나아감에 따라, 상이한 패터닝 기술이 생겨났다. 이러한 기술에는 스페이서 한정 더블 패터닝(spacer defined double patterning), 극자외선 리소그래피(EUV) 및 스페이서 한정 더블 패터닝과 결합된 EUV를 포함한다. 또한, 유도 자기-어셈블리(DSA)는 미래의 리소그래피 응용분야를 위한 옵션으로 고려되어 왔다. DSA는 블록 공중합체의 사용을 수반하여 자기-조립용 패턴을 한정한다. 사용된 블록 공중합체는 폴리메틸 메타크릴레이트(PMMA), 폴리스티렌, 또는 폴리스티렌-블록-메틸 메타크릴레이트(PS-b-PMMA)를 포함할 수 있다. 다른 블록 공중합체는 최근 떠오르는 "하이-키(high-Chi)" 고분자를 포함할 수 있으며, 이는 잠재적으로 작은 치수를 가능하게 할 수 있다.
상술한 패터닝 기술은 기판의 고 해상도 패터닝이 가능하도록 기판 상에 배치된 적어도 하나의 고분자 레지스트를 이용할 수 있다. 고 해상도 및 라인-에지 조도(line-edge roughness) 요건을 모두 만족시키기 위해, 고분자 레지스트는 일반적으로 얇은 층일 수 있다. 그러나, 이러한 얇은 고분자 레지스트는 몇 가지 단점을 가질 수 있다. 특히, 고 해상도 고분자 레지스트는 낮은 에칭 저항성을 가질 수 있다. 이렇게 낮은 에칭 저항성은 패터닝된 레지스트의 하부층으로의 이송을 더욱 어렵게 한다. 반도체 소자의 크기를 더 축소시키기 위해 필요한 진보된 고 해상도 고분자 레지스트가 극히 낮은 에칭 저항성 및 에칭 선택도를 갖는 경우, 낮은 에칭 저항성 문제는 더 심해진다. 또한, 고 해상도 고분자 레지스트는 얻어진 패턴에서 높은 에지 조도를 초래할 수 있다.
따라서, 고분자 레지스트의 패턴을 하드마스크(hardmask)에 이송하는 것이 유리할 수 있다. 하드마스크는 반도체 처리에서 고분자 또는 다른 유기 "소프트(soft)" 레지스트 재료 대신에 더 높은 에칭 저항성과 에칭 선택도를 갖는 에칭 마스크로서 사용된 재료이다. 그 결과, 진보된 특성을 갖는 하드마스크 시스템이 필요할 수 있다.
본 발명의 적어도 하나의 실시예에 따라서, 기판상에 구조물을 형성하는 방법이 제공된다. 상기 방법은:
반응 챔버에서 하드마스크 재료를 기판에 제공하는 단계; 및
하나 이상의 침투 사이클 동안에 상기 하드마스크 재료를 침투 재료로 침투시키는 단계를 포함한다. 상기 사이클은,
a) 상기 반응 챔버에서 제1 기간(T1) 동안 상기 기판 상의 하드마스크 재료에 제1 전구체를 제공하는 단계;
b) 상기 반응 챔버로부터 제2 기간(T2) 동안 상기 제1 전구체의 일부분을 제거하는 단계; 및
c) 제3 기간(T3) 동안 상기 기판 상의 하드마스크 재료에 제2 전구체를 제공해서, 상기 제1 전구체 및 제2 전구체가 서로 반응케 하여 상기 하드마스크 재료에 상기 침투 재료를 형성시키는 단계를 포함할 수 있다.
본 발명과 선행 기술에 비해 달성되는 장점들을 요약하기 위해, 본 발명의 특정 목적들 및 장점들이 전술 되었다. 물론, 모든 그러한 목적들 및 장점들이 본 발명의 임의의 특별한 실시예에 따라 반드시 달성되는 것이 아니라는 것을 이해하여야 한다. 따라서, 예들 들어 당업자는, 본 발명이, 본원에 교시 또는 제안될 수 있는 다른 목적들 또는 장점들을 반드시 달성하지 않고서, 본원에 교시되거나 제시된 바와 같은 하나의 장점 또는 여러 장점들을 달성 또는 최적화 하는 방식으로 구현되거나 수행될 수 있다는 것을 인식할 것이다.
이들 실시예들의 모두는 본원에 개시된 본 발명의 범주 내에 있도록 의도된다. 이들 및 다른 실시예들은 첨부된 도면들을 참조하는 특정 실시예들의 다음의 상세한 설명으로부터 당업자에게 용이하게 명백해 질 것이고, 본 발명은 개시된 임의의 특정 실시예(들)에 한정되지 않는다.
본원에 개시된 발명의 이러한 그리고 기타 특징, 양태 및 장점들은 특정 실시예의 도면을 참조하여 아래에 설명될 것이고, 이는 본 발명을 도시하기 위함이고, 본 발명을 한정하기 위함은 아니다.
도 1은 본 발명의 적어도 하나의 실시예에 따른 흐름도이다.
도 2는 본 개시의 다양한 예시적 실시예에 따른 예시적 시스템을 도시한다.
도 3은 본 개시의 다양한 예시적 실시예에 따른 추가적인 예시적 시스템을 도시한다.
도면의 구성 요소들은 간략하게 그리고 명료하게 도시되어 있으며, 도시된 본 개시의 실시예의 이해를 돕기 위해 반드시 축적대로 도시되지 않았음을 이해할 것이다. 예를 들어, 본 개시에서 도시된 실시예의 이해를 돕기 위해 도면 중 일부 구성 요소의 치수는 다른 구성 요소에 비해 과장될 수 있다.
특정 실시예 및 예시가 아래에 개시되었지만, 당업자는 본 발명이, 구체적으로 개시된 실시예 및/또는 본 발명의 용도 및 이들의 명백한 변형 및 균등물을 넘어 연장된다는 것을 이해할 것이다. 따라서, 개시된 본 발명의 범주는 후술되는 구체적으로 개시된 실시예에 의해 제한되지 않도록 의도된다.
본 발명에 따른 실시예들은 하드마스크의 막 침투 공정에의 조합에 관한 것이다. 하드마스크와 침투 공정의 이 조합은 하드마스크의 물성들(예, 에칭율 또는 심지어 패터닝된 피처의 폭에 대한 LER)을 상당히 변경할 수 있다.
도 1은 본 발명의 적어도 하나의 실시예에 따른 방법(100)을 도시한다. 상기 방법 (100)은 기판을 반응 챔버 내에 제공하는 제1 단계(110)를 포함하며, 상기 기판은 기판의 상부에 적어도 하나의 하드마스크 재료를 갖는다.
상기 하드마스크 재료는 다공성일 수 있다. 다공성도는 하드마스크 재료의 총 부피의 일부로서 하드마스크 재료 내의 빈 공간을 측정함으로써 측정될 수 있고 0 내지 1의 값을 가질 수 있다. 하드마스크 재료는, 총 부피에 걸친 빈 공간의 부분이 0.1보다 크거나, 0.2보다 크거나, 심지어 0.3보다 큰 경우 다공성으로서 적격화될 수 있다.
하드마스크 재료는, 예를 들어, 글래스 상의 스핀 또는, 탄소 층, 실리콘 질화물 층, 반사 방지 코팅 또는 비정질 탄소 막상의 스핀을 포함할 수 있다. 상기 글래스 상의 스핀 또는 탄소 층상의 스핀은 하드마스크 재료를 제공하도록 글래스 또는 탄소층을 기판상에 스피닝함으로써 제공될 수 있다. 또한, 하드마스크 재료는 SiCOH, 또는 SiOC를 포함할 수 있다.
일 실시예에서, 하나의 패턴층이 하드마스크 재료 위에 제공될 수 있고 그 패턴층의 패턴은 하드마스크 재료 내에서 식각되어 패턴닝된 하드마스크를 생성할 수 있다. 이어서, 패턴층은 제거될 수 있고, 패터닝된 하드마스크는 추가 가공을 위해 사용될 수 있다. 이는 고해상도 하드마스크 재료가, 보다 에칭 저항성인 하드마스크를 적용함으로써 낮은 에칭 저항을 가질 수 있는 문제를 완화시킬 수 있다. 하드마스크는 패터닝된 하드마스크의 라인 에지 조도 또는 라인 폭을 개선하기 위해 추가로 가공될 수 있다. 하드마스크와 패턴층 사이에 중간층이 있을 수 있다.
일 실시예에서, 패턴층은, 하드마스크 재료의 최상부 상에 레지스트(예를 들어, 광 레지스트)층을 제공하고 그 레지스트 층을 (광학) 리소그래피 장치로 패터닝함으로써 하드마스크 재료 상에 제공될 수 있다. 광 레지스트층은 낮은 에칭 저항을 가질 수 있고, 레지스트층의 패턴을 하드마스크로 이송함으로써 패턴의 에칭 저항성이 개선될 수 있다.
레지스트층은 어닐링될 수 있다. 어닐링 단계는 레지스트로부터의 수분 또는 다른 오염물을 탈가스(degassing)하거나, 레지스트를 경화시키거나, 또는 기판 표면으로부터 레지스트 부분들을 선택적으로 연소시키는 목적을 가질 수 있다.
일 실시예에서, 하드마스크 재료의 최상측의 패턴층이, 블록 공중합체 필름을 하드마스크 재료 위에 위치시키고 블록 공중합체 필름의 유도된 자기 어셈블리를 촉진시켜 패턴층을 형성함으로써 제공될 수 있다. 블록 공중합체 필름은 낮은 에칭 저항을 가질 수 있고, 공중합체의 패턴을 하드마스크로 이송함으로서 패턴의 에칭 저항성이 개선될 수 있다. 중간 패턴층은 블록 공중합체 필름을 유도하기 위해 필요한 경우 하드마스크 재료와 블록 공중합체 층 사이에 제공될 수 있다.
얻어진 패턴에서 낮은 결함 밀도에 도달하기 위해서 블럭 공중합체 필름의 자기-조립 어닐링이 수행되는 실시예에서, 어닐링 공정의 시간, 온도, 주위 조건들 그리고 압력과 같은 공정 변수가 중요할 수 있다. 낮은 결함 밀도를 얻기 위해 긴 어닐링 시간이 필요할 수 있다. 어닐링은 100°C 내지 400°C, 바람직하게는 200°C 내지 300°C 범위에서, 보다 바람직하게는 250°C의 온도에서 대략 60분 동안 일어날 수 있다. 원하는 어닐링의 양에 따라 기타 온도 및 지속 시간이 가능하다. 그러나, 자기-조립 어닐링 온도는 너무 높게 증가해서는 안되고, 높으면 고분자가 분해하기 시작할 수 있다.
어닐링이 행해지는 주위 환경은 질소, 아르곤, 헬륨, 수소, 산소, 오존, 수증기, 용매 증기 또는 이들 가스의 혼합을 포함할 수 있다. 어닐링 주위 환경의 압력은 초고진공으로부터 대기압 또는 심지어 대기압보다 높은 압력까지 범위의 임의의 압력일 수 있다.
본 발명의 일 실시예에 따라, 어닐링 공정은 단일 웨이퍼 핫 플레이트 상에서 일어날 수 있다. 본 발명의 다른 실시예에 따라, 배치식 반응기는 긴 어닐링 시간을 필요로 하는 공정에 유리할 수 있다. 배치식 반응기는 2 내지 250매 기판, 바람직하게는 5 내지 150매 기판, 또는 가장 바람직하게는 약 100매 기판을 수용할 수 있다. 예를 들어, 2개 이상의 반응 챔버를 포함하는 클러스터 툴이 작동되어 하나의 반응 챔버, 바람직하게는 하나의 배치식 방응기가 어닐링 공정을 위해 사용될 수 있다. 이것은 비용 절감적인 방법으로 1-2 시간 수준으로 긴 어닐링 시간을 수행시킬 수 있다.
방법(100)은, 하나 이상의 침투 사이클 동안 하드마스크 재료가 침투 재료로 침투될 수 있는 제2 단계(120)를 포함할 수 있다. 각각의 침투 사이클은 다음의 단계를 포함할 수 있다:
제1 기간(T1) 동안 반응 챔버 내 기판 상의 하드마스크 재료에 제1 전구체를 제공하는 단계(120a);
제2 기간(T2) 동안 제1 전구체의 일부를 제거하는 단계(120b); 그리고
제3 기간(T3) 동안 상기 기판 상의 상기 하드마스크 재료에 제2 전구체를 제공해서, 상기 제1 전구체 및 제2 전구체가 서로 반응하게 하여 상기 침투 재료를 형성시켜 하드마스크 재료의 보강부를 초래 하는 단계(120c)이다.
선택적으로, 침투 사이클은 제2 전구체의 일부가 제4 기간(T4) 동안 제거될 수 있는 단계(120d)를 가질 수 있다. 침투 시퀀스는 N 회 반복될 수 있는데, 여기서 N은 1 내지 60, 바람직하게는 3 내지 20, 가장 바람직하게는 5 내지 12이다. 침투(120)는 금속 또는 유전체를 형성하는 전구체가 하드마스크 재료를 침투할 수 있도록 수행될 수 있다. 전구체들은 바람직하게는 침투 동안 가스이다.
선택적으로, 금속 또는 유전체와 같은 침투 재료는 하드마스크의 전체 부피상에 또한 증착될 수 있다. 이는, 예를 들어, 패턴을 더욱 넓고 더 에칭 저항성으로 만들도록 하드마스크가 패터닝되는 경우에 수행될 수 있다.
또한, 자기 정렬된 더블 패터닝 마스크층을 하드마스크의 최상부에도 침투/증착시키는 것 또한 가능해 진다. 원래의 하드마스크층을 제거한 후, 더블 패터닝 마스크층이 추가 패턴 이송을 위해 사용될 수 있다.
제1 전구체 및/또는 제2 전구체를 제거하는 단계는, 제1 전구체 또는 제2 전구체를 반응 챔버 밖으로 펌핑함으로써, 그리고 선택적으로 또는 추가적으로 제1 전구체 및/또는 제2 전구체를 퍼지하기 위해서 반응 챔버 내에 퍼지 가스를 제공함으로써 달성될 수 있다.
제1 전구체는 단계(120a)에서 1 내지 20000, 바람직하게는 20 내지 6000, 보다 바람직하게는 50 내지 4000, 그리고 가장 바람직하게는 100 내지 2000 초 사이의 제1 기간(T1) 동안 제공될 수 있다. 이러한 방식으로, 제1 전구체의 하드마스크 재료 내로의 딥 침투가 보장된다.
단계(120b)에서 제1 전구체의 일부가 1 내지 20000, 바람직하게는 20 내지 6000, 보다 바람직하게는 50 내지 4000, 그리고 가장 바람직하게는 100 내지 2000 초 사이의 제2 기간(T2) 동안 제거될 수 있다.
단계(120)에서의 방법은 증착/침투 시스템(200, 도 2), (300, 도 3))에서 수행될 수 있다. 증착 시스템은 확산 오븐, 화학 기상 증착 시스템, 원자층 증착 시스템 또는 전용 연속 침투 합성 시스템일 수 있다. 상기 방법은 반응기 챔버를 20 내지 450℃바람직하게는 50 내지 150℃보다 바람직하게는 60 내지 110℃그리고 가장 바람직하게는 65 내지 95℃사이의 온도로 가열하는 단계를 포함할 수 있다.
이제 도 2를 참조하면, 하드마스크 재료의 적어도 일부를 침투시키기 위한 시스템(200)이 도시되어 있다. 상기 시스템(200)은 제1 반응 챔버(203), 기판 홀더(204) 및 가스 분배 시스템(206)을 더 포함할 수 있는 반응기(202)를 포함할 수 있다. 시스템(200)은 제1 전구체 소스(207); 제2 전구체 소스(208); 캐리어 또는 퍼지 가스 소스(210); 그리고 소스들(207, 208, 210, 216)과 반응기(202) 사이에 개재된 밸브들(211, 212, 214)를 더 포함할 수 있는 가스 전구체 이송 시스템(201)을 또한 포함할 수 있다.
반응 챔버(203)는 독립형 반응 챔버 또는 클러스터 툴의 부분일 수 있다. 또한, 반응 챔버(203)는 본원에서 설명된 침투 공정에 전용될 수 있거나, 반응 챔버(203)는 예를 들어 막 증착, 적어도 하나의 폴리머층의 일부 제거 및 하나 이상의 추가층 증착 및/또는 에칭 처리와 같은 다른 공정에 사용될 수 있다. 예를 들어, 반응 챔버(203)는 화학 기상 증착(CVD) 및/또는 원자층 증착(ALD) 처리를 위해 통상적으로 사용되는 반응 챔버를 포함할 수 있고 직접식 플라즈마 및/또는 원격식 플라즈마 장치를 포함할 수도 있다.
추가의 반응 챔버(203)가 진공 또는 거의 대기압 하에서 작동할 수 있다. 일례로서, 반응 챔버(203)는 적어도 하나의 기판 상으로 제1 전구체 및 제2 전구체를 순차적으로 펄스화함으로서 막의 ALD 증착에 적합한 반응 챔버를 포함할 수 있고, 상기 막은 적어도 제1 전구체의 하드마스크 재료내로의 침투가 가능하도록 구성된다. 시스템(200)에 적합한 예시적인 ALD 반응 챔버가 미국 특허 번호 제8,152,922에 기술되어 있으며, 그 내용이 본 개시와 충돌하지 않는 한 본원에 참고로 내용이 원용된다.
기판 홀더(204)는 기판 위에 배치된 하드마스크 층을 갖는 기판(216)과 같은 적어도 하나의 기판을 공정 처리 동안 정 위치에 유지하도록 구성될 수 있다. 추가적이거나 선택적으로, 기판 홀더(204)는 공정 처리 중에 (예를 들어, 가열 요소(205)에 의해) 가열되거나, 냉각되거나, 주위 공정 온도에 있을 수 있다. 일부 실시예들에서 가열 요소(205)는 상기 적어도 하나의 기판(216) 상에서 어닐링 단계를 수행하도록 구성될 수 있다.
가스 분배 시스템(206)이 블록 형태로 도시되어 있지만, 가스 분배 시스템(206)은 상대적으로 복잡할 수 있고, 가스 혼합물을 반응 챔버(203)의 나머지 부분에 분배하기 이전에 제1 전구체 소스(207), 제2 전구체 소스(208), 그리고 퍼지 가스 소스(210)로으로부터의 증기(가스)를 혼합하도록 디자인될 수 있다. 또한, 가스 분배 시스템(206)은 반도체 표면으로 수직의(도시된 바와 같음) 또는 수평의 가스 흐름을 제공하도록 구성될 수 있다. 예시적인 가스 분배 시스템은 미국 특허 제8,152,922호에 기술되어 있다.
제1 전구체 소스(207)는 침투 공정에 적합한 물질을 함유하는 금속의 액체, 고체 또는 가스 소스일 수 있다. 제1 전구체 소스(207)가 액체 또는 고체인 경우, 소스 재료는 반응 챔버(203)에 들어가기 전에 기화될 수 있다.
제2 전구체 소스(208)는 침투 공정에 적합한 물질을 함유하는 액체, 고체 또는 가스 소스일 수 있다. 제2 전구체 소스(208)가 액체 또는 고체인 경우, 소스 재료는 반응 챔버(203)에 들어가기 전에 기화될 수 있다.
제1 전구체 및 제2 전구체는 하드마스크를 증착 및/또는 침투시키는데 같이 활용될 수 있다. 예를 들어, 일부 실시예들에서, 시스템(200)은 하드마스크 상에 및/또는 그 안에 산화 알루미늄(Al2O3), 산화 실리콘,(SiO2), 질화 실리콘(SiN), 산질화 실리콘(SiON), 탄질화 실리콘(SiCN), 탄화 실리콘(SiC), 탄화 티탄(TiC), 질화 알루미늄(AlN), 질화 티탄(TiN), 질화 탄탈륨(TaN), 텅스텐(W), 코발트(Co), 산화 티탄(TiO2), 산화 탄탈륨(Ta2O5), 산화 지르코늄(ZrO2) 또는 산화 하프늄(HfO2)을 증착 및/또는 침투시키도록 구성될 수 있다.
퍼지 가스 소스(210)는 제1 전구체 소스(207) 및/또는 제2 전구체 소스(208)를 퍼지하기에 적합한 임의의 적합한 가스를 포함할 수 있다. 캐리어 또는 퍼지 가스 소스(210)는 증착 및/또는 침투 공정 이전, 이후 또는 동안에 반응 챔버(203)를 퍼지하는 데 적합한 임의의 가스를 포함할 수 있다. 본 개시의 예시적인 실시예에 따라 퍼지 가스는 질소, 아르곤, 헬륨, 또는 이들의 조합일 수 있다.
도 2에 도시된 바와 같이, 소스들(207, 208, 및 210)은 밸브(211, 212, 및 214)를 통해 반응 챔버(203)와 유체 연통하며, 이들 밸브들은 공급원 라인(219, 220 및 222)을 사용하여 반응 챔버(203)로 각각의 소스 재료의 흐름, 혼합 및 분배를 제어하는 데 사용될 수 있다.
본 개시의 추가적 실시예에서, 하드마스크를 증착 및/또는 침투시키기 위한 시스템 (300)이 도 3을 참조하여 도시된다. 시스템(300)은 시스템(200)의 것과 유사할 수 있지만, 제1 반응 챔버(203A) 및 제2 반응 챔버(203B)를 더 포함할 수 있는 반응기(302)를 포함할 수 있다. 비록 도 3은 2개의 반응 챔버를 포함하는 반응기(302)를 도시하지만, 일부 실시예에서는 반응기(302)가 복수의 반응 챔버를 포함할 수 있는바, 각 반응 챔버는 이전에 본원에 기술된 바와 같이 기판 홀더(204), 및 가스 분배 시스템(206)을 포함함을 인정해야 한다. 기판 홀더는 단일 기판, 2 내지 25매의 기판(미니 배치) 또는 26 내지 200매의 기판(풀 배치)을 유지하도록 구성될 수 있다. 시스템(300)은 또한 제1 전구체 소스(207); 제2 전구체 소스(208); 캐리어 또는 퍼지 가스 소스(210); 소스들(207, 208, 210)과 반응기(302) 사이에 개재된 밸브들(211, 212, 214)을 포함할 수 있다.
시스템(300)은 또한 기판, 예를 들어 반도체를 제1 반응 챔버(203A) 및 제2 반응 챔버(203B)로부터 시스템 외부로 이송하는데 활용되는 이송 시스템(304)을 포함할 수 있다. 일부 실시예들에서, 반응 챔버들(203A 및 203B)은 본원에서 설명된 침투 공정에 전용될 수 있거나, 반응 챔버들(203A 및 203B)은 예를 들어 층 증착 및/또는 에칭 공정과 같은 다른 공정에도 사용될 수 있다. 예를 들어, 반응 챔버들(203A 및 203B)은 본원에 기술된 바와 같이 화학 기상 증착(CVD), 침투 및/또는 원자층 증착 공정에 통상적으로 사용되는 반응 챔버를 포함할 수 있다. 추가적인 실시예에서, 시스템(300)은 증착 및 에칭 공정과 같은 추가적인 전용 공정을 수행하기 위한 추가의 반응 챔버를 포함할 수 있다.
도 3에 도시된 바와 같이, 소스들(207, 208)은 밸브들(211, 212)를 통해 반응기(302)와 유체 연통하며, 그 밸브들은 공통의 전구체 공급 시스템(201)의 모든 부분과 공급원 라인들(219, 220)을 사용하여 반응 챔버들(203A, 203B)로의 각각의 원료 물질의 흐름, 혼합 및 분배를 제어하는 데 사용될 수 있다. 방법은 기판을 각각의 반응 챔버에 제공하는 단계 및 공통 전구체 이송 시스템(201)으로 적어도 2개의 반응 챔버에 제1 전구체 및/또는 제2 전구체를 제공하는 단계를 포함한다.
시스템은 공통 전구체 제거 시스템(226)(예, 진공 펌프)을 포함할 수 있다. 방법은 공통 제거 시스템(226)으로 적어도 2개의 반응 챔버로부터 제1 전구체 또는 제2 전구체를 제거하는 단계를 더 포함할 수 있다.
시스템은 공통 퍼지 시스템들(210, 214, 222)을 포함할 수 있다. 방법은 공통 퍼지 시스템으로 퍼지 가스를 제공하여 적어도 2개의 반응 챔버로부터 제1 전구체 또는 제2 전구체를 제거하는 단계를 포함할 수 있다.
일 실시예에서 도 2의 시스템(200)의 반응 챔버는, 도 1의 단일 기판(21)을 수용하도록 구성되고 배열되며, 제1 전구체는 1 내지 20000, 바람직하게는 20 내지 4000, 더욱 바람직하게는 30 내지 1000 초 사이의 제1 기간(T1) 동안 제공될 수 있다.
추가적인 실시예에서 시스템의 반응 챔버는 2 내지 25매의 기판을 수용하도록 구성되고 배열되며, 제1 전구체는 1 내지 16000, 바람직하게는 20 내지 7000, 가장 바람직하게는 30 내지 1500 초 사이의 제1 기간(T1) 동안 제공될 수 있다.
다른 실시예에서 반응 챔버는 26 내지 200매의 기판을 수용하도록 구성되고 배열되며, 제1 전구체는 1 내지 20000, 바람직하게는 100 내지 10000, 더욱 바람직하게는 200 내지 6000, 그리고 가장 바람직하게는 300 내지 4000 초 사이의 제1 기간(T1) 동안 제공될 수 있다.
침투 재료로 패턴된 하드마스크 재료를 침투시키기 전에, 탈가스를 향상시키기 위해 반응 챔버(들)를 1 내지 3000초, 바람직하게는 120 내지 1200초 동안 20 및 600 °C, 바람직하게는 50 및 150 °C, 그리고 가장 바람직하게는 70 및 100°C 사이의 온도로 퍼지하는 것이 유리할 수 있다.
단계(120a)에서 제1 전구체는 제1 주기(T1) 동안 버블러(bubbler)가 제공될 수 있으며, 이는 0.1 내지 20, 바람직하게는 0.3 내지 1 초 동안의 퍼지 가스 펄스와 교대하면서, 0.1 내지 100, 바람직하게는 1 내지 3 초 동안의 퍼지 가스와 혼합된 제1 전구체의 펄스를 갖는 불연속인 제1 전구체 흐름을 제공한다.
제1 전구체를 반응 챔버로 제공하기 이전에, 제1 전구체는 반응 챔버 압력에서 실온 내지 끓는점 사이의 온도로, 바람직하게는 20 내지 450℃보다 바람직하게는 30 내지 80℃및 보다 더 바람직하게는 35 내지 60℃의 온도로 가열될 수 있다. 침투 시스템은, 반응 챔버 내의 온도를 20 내지 450℃바람직하게는 50 내지 150℃보다 바람직하게는 60 내지 110℃그리고 가장 바람직하게는 65 내지 95℃사이의 온도로 제어하기 위해 제어기, 히터 및 온도 센서를 포함하는 온도 제어 시스템을 구비할 수 있다. 반응기 챔버(들)는 20 내지 450 ℃바람직하게는 50 내지 150℃보다 바람직하게는 60 내지 110℃가장 바람직하게는 65 내지 95℃사이의 온도로 가열될 수 있다. 반응기 챔버(들)의 모든 표면들, 배기 라인(들) 및 밸브들은 20 내지 450℃바람직하게는 50 내지 150℃보다 바람직하게는 60 내지 110℃가장 바람직하게는 65 내지 95℃의 온도로 가열될 수 있어서 시스템 내의 전구체 중 적어도 하나의 응축을 피하도록 한다.
증착 시스템은 반응 챔버 내의 압력을 조절하기 위해 제어기, 펌프 및 퍼지 가스 또는 제1 전구체 공급부를 포함하는 압력 제어 시스템을 구비할 수 있다. 챔버 내의 압력은 0.001 내지 1000 Torr, 바람직하게는 1 내지 400 Torr, 보다 바람직하게는 5 내지 100 Torr, 그리고 가장 바람직하게는 10 내지 50 Torr 사이의 값으로 제어될 수 있다.
침투 재료는 금속을 포함할 수 있다. 제1 전구체는 트리메틸 알루미늄(TMA), 트리에틸 알루미늄(TEA) 및 디메틸알루미늄하이드라이드(DMAH)로 이루어진 그룹으로부터 선택된 알루미늄의 알킬 화합물일 수 있고 침투 재료는 금속으로서 알루미늄을 포함한다.
제1 전구체 또는 제2 전구체는 티타늄(IV)클로라이드(TiCl4), 탄탈륨(V)클로라이드(TaCl5), 니오븀 염화물(NbCl5)을 포함할 수 있다. 제2 전구체는 산화제일 수 있다. 상기 산화제는 물, 오존, 수소페록사이드, 암모니아 및 히드라진을 포함하는 그룹으로부터 선택된다.
지르코늄 또는 하프늄의 침투를 위해서, Zr 또는 Hf 전구체는 금속 유기물, 유기 금속 또는 할라이드 전구체를 포함할 수 있다. 일부 실시예들에서 전구체는 할라이드이다. 일부 다른 실시예들에서 전구체는 TEMAZ 또는 TEMAH와 같이 Hf 또는 Zr의 알킬아민 화합물이다.
제2 단계(120)에서 증착된 금속 또는 유전체는, 알루미늄 산화물(Al2O3), 실리콘 이산화물(SiO2), 실리콘 질화물(SiN), 실리콘 산탄화물(SiOC), 실리콘 탄질화물(SiCN), 실리콘 탄화물(SiC), 알루미늄 질화물(AlN), 티타늄 질화물(TiN), 티타늄 탄화물(TiC), 탄탈륨 질화물(TaN), 텅스텐(W), 코발트(Co), 티타늄 이산화물(TiO2), 탄탈륨 산화물(Ta2O5), 지르코늄 이산화물(ZrO2), 또는 하프늄 이산화물(HfO2)을 포함할 수 있다.
선택적 증착을 수행하기 위해서, 상기 금속을 얻기 위한 전구체는 알루미늄 산화물(Al2O3, AlO) 형성을 위해 트리메틸알루미늄(TMA) 및 물(H2O)과 같은 것이 사용될 수 있다. 제2 단계(120)에서의 침투 및/또는 증착은 알루미늄 산화물 형성을 위해 20 내지 300℃의 온도 범위, 바람직한 온도 범위인 65 내지 95℃에서 일어날 수 있다. 제2 단계(120) 동안의 온도는 전단계 동안의 온도 미만일 수 있어서, 예시적 어닐링 온도 또는 탈가스 온도인 250℃에서 70 내지 100℃의 제3 단계(130) 온도까지 내려가기 위해 냉각 단계가 필요할 수 있다. 선택적인 어닐링 또는 탈가스 공정의 온도는 제2 단계(120) 온도 보다 적어도 25℃높을 수 있고, 바람직하게는 제2 단계(120) 온도 보다 제 25-300℃사이로 높을 수 있고, 보다 바람직하게는 제2 단계(120) 온도 보다 100-250℃높을 수 있다.
단계(120a)는 1 내지 20000 초, 바람직하게는 22 내지 6000 초, 보다 바람직하게는 50 내지 4000 초, 그리고 가장 바람직하게는 100 내지 2000초 사이의 제1 기간(T1) 동안 TMA와 같은 제1 전구체의 공급을 포함할 수 있다. 단계(120b)는 이어서 1 내지 20000 초, 바람직하게는 20 내지 6000 초, 보다 바람직하게는 50 내지 4000 초, 그리고 가장 바람직하게는 100 내지 2000 초 사이의 제2 기간(T2) 동안 제거 및/또는 퍼지를 또한 포함할 수 있다.
단계(120c)는 이후 1 내지 10000 초, 바람직하게는 6 내지 800 초, 보다 바람직하게는 10 내지 100 초 범위의 제3 기간(T3) 동안 물과 같은 제2 전구체의 공급을 포함할 수 있다. 제2 단계(120d)는 이후 1 내지 10000초, 바람직하게는 6 내지 800초 범위의 제4 기간(T4)의 제2 제거/퍼지를 포함할 수 있다.
또한, 제2 단계(120)는 금속 또는 유전체의 충분한 침투를 얻기 위해 필요에 따라 반복될 수 있다.
본 발명의 적어도 하나의 실시예에 따라, 침투의 제2 단계(120)는 어닐링의 선택적 단계를 선행할 수 있다. 이 경우, 금속 또는 유전체막은 먼저 하드마스크 재료를 침투시키고 나서 어닐링 공정이 발생할 수 있다. 본 발명의 적어도 하나의 실시예에서, 선택적인 어닐링 단계 및 침투의 제2 단계(120)가 주위 공기에 노출되지 않고 일어난다. 주위 대기에 노출이 되지 않는 것은 실질적으로 많은 양의 산소 또는 물에 노출되는 것을 피한다. 주위 공기에의 노출은 잠재적으로 물을 흡수함으로써 영향을 받을 수 있는 하드마스크 재료의 침투에 악영향을 미칠 수 있다. 하드마스크 재료가 물을 흡수하면, 원하지 않는 물질의 증착이 초래될 수 있다.
일 실시예에 따르면, 침투 재료는, 티타늄(IV)클로라이드(TiCl4), 탄탈륨(V)클로라이드(TaCl5), 및 니오븀 염화물(NbCl5)로 구성되는 그룹으로부터 선택되는 금속 할라이드인 제1 전구체, 그리고 트리메틸 알루미늄(TMA), 트리에틸 알루미늄(TEA), 및 디메틸알루미늄하이드라이드(DMAH), 디메틸에틸아민알레인(DMEAA), 트리메틸아민알레인(TEAA), N-메틸피로리딘알레인(MPA), 트리-이소부틸알루미늄(TIBA), 트리터트부틸알루미늄(TTBA), 트리메틸붕소 및 트리에틸붕소로 이루어진 그룹으로부터 선택된 붕소 탄화수소 화합물 또는 알루미늄인 제 2전구체에 의해 제조된 금속 탄화물을 포함한다.
도시되고 설명된 구체적인 적용예는 본 발명의 예시이자 최적 실시모드이며, 어떤 방식으로도 양태와 적용예의 범주를 달리 제한하도록 의도되지 않는다. 실제로, 간결성을 위해서, 시스템의 종래의 제조, 연결, 준비 및 다른 기능적 양태는 상세히 기술되지 않을 수 있다. 또한, 다양한 도면들에서 도시된 연결선들은 다양한 요소들 사이의 예시적인 기능 관계 및/또는 물리적 결합을 표시하려는 의도이다. 많은 선택적인 또는 추가적인 기능적 관계 또는 물리적 연결은 실질적인 시스템에 존재할 수 있고/있거나 일부 실시예들에서는 없을 수 있다.
본원에 기술된 구성 및/또는 접근법은 본질적으로 예시적인 것이며, 다양한 변형이 가능하기 때문에, 이들 특정 구현예 또는 실시예가 제한적인 의미로 고려되어서는 안 된다는 것을 이해해야 한다. 본원에 설명된 특정 루틴 또는 방법은 임의의 처리 전략 중 하나 이상을 나타낼 수 있다. 따라서, 도시된 다양한 동작은 도시된 시퀀스에서, 상이한 시퀀스에서 수행되거나, 경우에 따라 생략될 수 있다.
본 개시의 요지는 본원에 개시된 다양한 공정, 시스템, 및 구성, 다른 특징, 기능, 행위 및/또는 성질의 모든 신규하고 비자명한 조합 및 하위조합뿐만 아니라 임의의 그리고 모든 이들의 등가물들을 포함한다.

Claims (23)

  1. 기판 상에 구조물을 형성하는 방법으로서,
    반응 챔버에서 기판에 하드마스크 재료를 제공하는 단계; 및
    하나 이상의 침투 사이클 동안에 하드마스크 재료를 침투 재료로 침투 시키는 단계를 포함하고, 상기 사이클은:
    a)상기 반응 챔버에서 제1 기간(T1) 동안 기판 상의 상기 침투 재료에 제1 전구체를 제공하는 단계;
    b)상기 반응 챔버로부터 제2 기간(T2) 동안 상기 제1 전구체의 일부분을 제거하는 단계; 및,
    c)제3 기간(T3) 동안 상기 기판 상의 하드마스크 재료에 제2 전구체를 제공해서, 상기 제1 전구체 및 제2 전구체가 서로 반응하게 하여 하드마스크 재료에 침투 재료를 형성시키는 단계를 포함하는, 구조물을 형성하는 방법.
  2. 제1항에 있어서, 상기 방법은:
    하드마스크 재료 위에 패턴층을 제공하는 단계; 그리고,
    하드마스크 재료의 패턴층의 패턴을 에칭하여 패턴된 하드마스크(hardmask)를 생성하는 단계를 포함하는, 구조물을 형성하는 방법.
  3. 제2항에 있어서, 상기 하드마스크 재료 위에 상기 패턴층을 제공하는 단계는:
    상기 하드마스크 재료 상에 포토레지스트층을 제공하는 단계; 그리고,
    리소그래피 장치로 상기 포토레지스트층을 패터닝하는 단계를 포함하는, 구조물을 형성하는 방법.
  4. 제2항에 있어서, 상기 하드마스크 재료 위에 패턴층을 제공하는 단계는,
    하드마스크 재료 상에 블록 공중합체 필름을 제공하는 단계; 그리고,
    상기 블록 공중합체 필름의 유도된 자기 조립체를 촉진해서 상기 패턴층을 형성하는 단계를 포함하는, 구조물을 형성하는 방법.
  5. 제1항에 있어서, 상기 하나 이상의 침투 사이클은:
    d)제4 기간(T4) 동안 제2 전구체의 일부를 제거하는 단계를 포함하고; 상기 하나 이상의 침투 사이클은 1 내지 60 사이클의 침투 사이클인, 구조물을 형성하는 방법.
  6. 제1항에 있어서, 상기 마스크 재료는 다공성인, 구조물을 형성하는 방법.
  7. 제1항에 있어서, 상기 하드마스크 재료는 글래스 상의 스핀(spin) 또는 탄소층 상의 스핀(spin)을 포함하는, 구조물을 형성하는 방법.
  8. 제1항에 있어서, 상기 상부 하드마스크 재료는 실리콘 질화층을 포함하는, 구조물을 형성하는 방법.
  9. 제1항에 있어서, 상기 하드마스크 재료는 반사 방지 코팅을 포함하는, 구조물을 형성하는 방법.
  10. 제1항에 있어서, 상기 하드마스크 재료는 비정질 탄소, SiCOH, 또는 SiOC 재료를 포함하는, 구조물을 형성하는 방법.
  11. 제1항에 있어서, 상기 제1 전구체 및/또는 제2 전구체를 제거하는 단계는 상기 제1 전구체 또는 상기 제2 전구체를 상기 반응 챔버 밖으로 펌핑하는 단계를 포함하는, 구조물을 형성하는 방법.
  12. 제1항에 있어서, 상기 제1 전구체 및/또는 제2 전구체를 제거하는 단계는 상기 제1 전구체 및/또는 제2 전구체를 제거하기 위해 상기 반응 챔버 내에 퍼지 가스를 제공하는 단계를 포함하는, 구조물을 형성하는 방법.
  13. 제1항에 있어서, 상기 방법은:
    각각 단일 기판을 수용하도록 구성되고 배치된 적어도 2개의 반응 챔버를 포함하는 순차적 침투 합성 장치를 제공하는 단계;
    각 반응 챔버에 기판을 제공하는 단계; 그리고,
    공통 전구체 이송 시스템으로 적어도 2개의 반응 챔버에 제1 전구체 및/또는 제2 전구체를 제공하는 단계를 포함하는, 구조물을 형성하는 방법.
  14. 제1항에 있어서, N회의 침투 사이클 동안 침투 재료로 하드마스크 재료를 침투시키기 전에, 반응 챔버는 20 내지 600℃사이의 온도에서 1 내지 3000초 동안 퍼징되는, 구조물을 형성하는 방법.
  15. 제1항에 있어서, 상기 밥법은 반응 챔버를 20 내지 450℃사이의 온도로 가열시키는 단계를 포함하는, 구조물을 형성하는 방법.
  16. 제1항에 있어서, 상기 방법은, 반응기 챔버의 모든 표면들, 배기 라인 및 밸브들을 20 및 450℃사이의 온도로 가열하는 단계를 포함하는, 구조물을 형성하는 방법.
  17. 제1항에 있어서, 상기 챔버 내 압력은 0.001 내지 1000 Torr인, 구조물을 형성하는 방법.
  18. 제1항에 있어서, 상기 침투 재료는 금속을 포함하는, 구조물을 형성하는 방법.
  19. 제18항에 있어서, 상기 제1 전구체 또는 상기 제2 전구체는 트리메틸 알루미늄(TMA), 트리에틸 알루미늄(TEA), 및 디메틸알루미늄하이드라이드(DMAH)로 이루어진 군으로부터 선택된 알루미늄의 알킬 화합물이고, 상기 침투 재료는 금속으로서 알루미늄을 포함하는, 구조물을 형성하는 방법.
  20. 제18항에 있어서, 상기 제1 전구체 또는 제2 전구체는 티타늄(IV)클로라이드(TiCl4), 탄탈륨(V)클로라이드(TaCl5), 니오븀 염화물(NbCl5)을 포함하는, 구조물을 형성하는 방법.
  21. 제1항에 있어서, 상기 제1 전구체 또는 상기 제2 전구체가 물, 오존 또는 과산화수소를 포함하는 군으로부터 선택된 산화제, 또는 암모니아 및 하이드라진을 포함하는 군으로부터 선택된 니트리디저인, 구조물을 형성하는 방법.
  22. 제18항에 있어서, 상기 침투 재료는, 티타늄(IV)클로라이드(TiCl4), 탄탈륨(V)클로라이드(TaCl5), 및 니오븀 클로라이드(NbCl5)로 구성되는 군으로부터 선택되는 금속 할라이드를 포함하는 제1 전구체 및 제2 전구체 중 하나, 그리고 트리메틸알루미늄(TMA), 트리에틸 알루미늄(TEA), 디메틸알루미늄하이드라이드(DMAH), 디메틸에틸아민알레인(DMEAA), 트리메틸아민알레인(TEAA), N-메틸피로리딘알레인(MPA), 트리-이소부틸알루미늄(TIBA), 트리터트부틸알루미늄(TTBA), 트리메틸붕소 및 트리에틸붕소로 이루어진 으로 이루어진 군으로부터 선택되는 붕소 탄화수소 화합물 또는 알루미늄을 포함하는 상기 제1 전구체 및 제2 전구체 중의 다른 하나에 의해 생성된 금속 탄화물을 포함하는, 구조물을 형성하는 방법.
  23. 제1항에 있어서, 상기 하드마스크 재료가 패터닝된, 구조물을 형성하는 방법.
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