KR20180131437A - 수소 플라즈마를 사용한 원자층 에칭 방법 - Google Patents

수소 플라즈마를 사용한 원자층 에칭 방법 Download PDF

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KR20180131437A
KR20180131437A KR1020180060822A KR20180060822A KR20180131437A KR 20180131437 A KR20180131437 A KR 20180131437A KR 1020180060822 A KR1020180060822 A KR 1020180060822A KR 20180060822 A KR20180060822 A KR 20180060822A KR 20180131437 A KR20180131437 A KR 20180131437A
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target layer
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마사루 자이츠
노부요시 고바야시
아키코 고바야시
마사루 호리
다카요시 츠츠미
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에이에스엠 아이피 홀딩 비.브이.
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Abstract

건식 에칭 공정에 의해 기판 상의 타겟 층을 에칭하는 방법은 적어도 하나의 에칭 사이클을 포함하며, 상기 에칭 사이클은: 기판 상의 타겟 층 상에 반응성 종을 사용하여 카본 할라이드 막을 증착하는 단계; 비-할로겐 수소-함유 에칭 가스의 플라즈마를 사용하여 타겟 층을 실질적으로 에칭하지 않고 카본 할라이드 막을 에칭함으로써 카본 할라이드 막의 경계 영역에서 에천트 종으로서 수소 할라이드를 생성하고, 경계 영역에서 타겟 층의 일부분을 에칭하는 단계를 포함한다.

Description

수소 플라즈마를 사용한 원자층 에칭 방법{Method of Atomic Layer Etching Using Hydrogen Plasma}
본 발명은 일반적으로 예를 들어, 실리콘 또는 금속 산화물로 구성된 층의 순환 건식(cyclic dry) 에칭 방법에 관한 것이다.
원자층 에칭(ALE : Atomic layer etching)은, 일본 특허 공개 공보 제 2013-235912호 및 제 2014-522104호에 개시되어 있는 바와 같이, 타겟 막 상에 흡착된 에천트(etchant) 가스를 사용하는 순환, 원자층 레벨 에칭이고, 여기된 반응성 종(reaction species)과 반응한다. 종래의 에칭 기술과 비교하여, ALE는 미세하고 좁은 볼록-오목 패턴을 형성하기 위해 서브 나노미터 오더(sub-nanometer order)의 정밀한 원자층 레벨 연속 에칭을 수행할 수 있으며, 예를 들어 더블 패터닝 공정에 적합할 수 있다. 에천트 가스로서, Cl2, HCl, CHF3, CH2F2, CH3F, H2, BCL3, SiCl4, Br2, HBr, NF3, CF4, C2F6, C4F8, SF6, O2, SO2 및 COS 등이 공지되어 있다. 그러나, 실리콘 산화막과 같은 산화물 미네랄 막을 에칭할 때, ALE에 의한 기판 상의 막에 대한 에칭의 평면내(in-plane) 균일성은 만족스럽지 않은 것으로 밝혀졌다.
에천트 가스로서 Cl2를 사용하는 ALE에 의해 Si 또는 GaAs를 에칭할 때, 비교적 양호한 평면내 에칭의 균일성이 얻어질 수 있다. 그러나, 에천트 가스로서 C4F8과 같은 플루오로카본(fluorocarbon)을 사용하는 ALE에 의해 실리콘 산화막을 에칭할 때, 에칭의 양호한 평면내 균일성이 얻어지지 않는다. 이는 통상적으로 에천트 가스의 흡착을 때때로 "화학 흡착(chemisorption)"으로 불리는 사실에도 불구하고, 화학적 흡착이 아니라 물리적 흡착을 통해 기판의 표면에 에천트 가스가 흡착되기 때문이다. 즉, 종래의 ALE는 표면에 물리적으로 흡착된 에 천트 가스에 의해 금속 또는 실리콘 산화막을 에칭하고, 여기서 흡착된 에천트 가스는 여기된 종과 반응하고, 또한 퍼지 후 반응 공간에 잔류하는 에천트 가스에 의해, 기상 에칭이 유발된다. 그 결과, 에칭의 평면내 균일성이 악화된다. 에천트 가스가 기판의 표면 상에 화학 흡착되는 경우, 흡착은 자기 제한(self-limiting) 흡착 반응 공정인, 화학적 포화 흡착인 "화학 흡착"이며, 여기서 증착된 에천트 가스 분자의 양은 반응성 표면 사이트(site)의 수에 의해 결정되고 포화 후 전구체(precursor) 노출과 무관하며, 에천트 가스의 공급은 반응성 표면 사이트가 사이클 당 포화되도록 한다(즉, 사이클 당 표면 상에 흡착된 에천트 가스는 원칙적으로 1 분자 두께를 갖는다). 기판 표면 상에 에천트 가스의 화학 흡착이 발생하면, 에칭의 높은 평면내 균일성이 달성될 수 있다. 종래의 ALE는, 흡착을 "화학 흡착"으로 부르지만, 사실상 물리적 흡착에 의해 기판 표면(예를 들어, SiO2 및 SiN) 상의 에천트 가스를 흡착한다. 에천트 가스의 흡착이 화학 흡착인 경우, 에칭의 평면내 균일성은 논리적으로 높고 또한 사이클 당 에칭률은 에천트 가스의 유량 또는 표면이 에천트 가스 분자에 의해 포화된 후 에천트 가스 흐름의 펄스 지속시간에 영향을 받지않아야 한다. 그러나, 종래의 에천트 가스 중 어느 것도 상기 요건을 충족시키지 않는다.
종래기술과 관련된 문제 및 해결책에 대한 상기의 및 임의의 다른 논의는 단지 본 발명에 대한 맥락을 제공하기 위한 목적에 대해서만 본 개시에 포함되었고, 그 논의의 임의의 또는 전부가 본 발명이 이루어진 당시에 공지되었다는 것을 인정하는 것으로 간주해서는 안된다.
일부 구현예에서, 에천트의 성분으로 구성된 막("에천트 막"으로 지칭될 수 있음)은 타겟 층의 표면 상에 증착되고, 그 다음 타겟 층 뿐만 아니라 에천트 막은 플라즈마 처리를 사용하여 에칭된다. 증착 단계 및 에칭 단계를 수행하고 필요에 따라 이들을 번갈아 반복함으로써, 타겟 층은 증착 단계 및 에칭 단계를 에칭 사이클로서 수행할 때마다 실질적으로 일정한 미리 결정된 양만큼 에칭될 수 있다. 상기에서, 에천트 성분은 초기에 타겟 층을 에칭하는 에천트 가스로서의 역할을 하지 않고, 타겟 층의 표면 상에 막을 형성한다. 본 개시에서, "막"은 실질적으로 핀홀(pinhole)이 없는 두께 방향에 수직인 방향으로 연속적으로 연장되어 전체 타겟 또는 타겟의 관련 표면을 커버하는 층을 지칭하며, 통상적으로 막은 표면 상에 가스 분자의 화학적 또는 물리적 흡착에 의해 단순히 형성되는 것이 아니라 반응성 종을 사용하는 반응을 통해 형성되고; 따라서, 막은 증착 공정이 계속됨에 따라 원자층 두께를 초과하는 두께 방향으로 성장할 수 있다. 또한, "막 증착"은 단지 타겟 층 표면 상에 반응성 사이트를 제공하는 것이 아니라, 특정 두께를 갖는 막을 물리적으로 증착하는 것이다.
일부 구현예에서, 타겟 층의 표면 상에 증착된 에천트 막이 수소 플라즈마와 같은 반응성 이온에 의해 에칭될 때, 에천트 막의 성분은 해리되고 반응성 이온과 반응하여, 에천트 막과 타겟 층 사이의 경계에서 타겟 층의 일부분을 에칭할 수 있는 반응성 에천트 종을 생성한다. 상기에서, 경계 부근에서 반응성 에천트 종을 생성할 필요가 있기 때문에, 경계에서 에천트 막의 특정 두께만이 타겟 층의 에칭 반응에 기여할 수 있다. 또한, 에천트 막을 에칭하는 반응성 이온이 타겟 층을 에칭하지 않기 때문에, 반응 이온에 의해 에천트 막이 제거되면, 타겟 층의 에칭 반응은 정지된다. 따라서, 상기 방법에 의해, 일정량의 타겟 층이 1회의 에칭 사이클에 의해 항상 에칭될 수 있으므로, 에칭 공정의 제어성 및 조작성이 높아진다.
예를 들어, 타겟 층이 SiO2로 구성된 경우, 타겟 층의 표면에 플루오로카본 막(CF 막) 이 플라즈마-강화 CVD 또는 열적 CVD에 의해 타겟 층의 표면 상에 에천트 막으로서 증착된 후, 에천트 막을 제거함과 동시에 타겟 층의 표면을 에칭하기 위해, 에천트 막을 수소 플라즈마에 노출시킨다. 상기에서, "동시에"는 실질적으로 또는 우세하게 동시에, 또는 실질적으로 또는 우세하게 시간상으로 중복되어 발생하는 것을 지칭한다. 상기에서, 타겟 층의 에칭된 부분의 깊이는 에천트 막의 두께가 증가함에 따라 증가하고; 그러나, 에칭된 부분의 깊이는 고평부(plateau)에 도달하고, 에천트 막의 두께가 특정 값에 도달할 때 더 이상 증가하지 않는다. 유사하게, 타겟 층의 에칭된 부분의 깊이는 에천트 막이 플라즈마에 노출되는 지속시간이 증가함에 따라 증가한다; 그러나, 에칭된 부분의 깊이는 고평부에 도달하고 플라즈마에 대한 에천트 막의 노출 시간이 특정 값에 도달할 때 더 이상 증가하지 않는다. 즉, 일부 구현예에서, 상기 논의된 에칭 공정은 포화점을 가지는 2개의 파라미터를 갖는 자기 제한 반응 공정이다.
상기에서, CF 막은 CH4, HF 등의 가스로서 수소 플라즈마에 의해 제거되며, SiO2 층의 표면 부근의 영역에서, SiO2 층의 일부분 또한 SiF4, H2O 등의 가스로서 동시에 제거된다. 경계 근처의 CF 막의 일부분만이 SiO2 층의 일부를 제거하는 데 기여하고, CF 막의 나머지 부분은 SiO2 층의 제거에 기여하지 않지만, 수소 플라즈마에 의해 간단하게 제거된다. 따라서, SiO2 층의 에칭된 부분의 깊이는 CF 막의 두께와 관련하여 고평부에 도달한다. 또한, 수소 플라즈마를 사용한 SiO2 층의 에칭이 CF 막이 존재할 때만 효과적이기 때문에, CF 막이 제거(소모)되면, SiO2 층의 에칭이 정지되며, 즉, SiO2 층의 에칭된 부분의 깊이는 또한 수소 플라즈마 노출 지속시간과 관련해서 고평부에 도달한다.
일부 구현예에서, 타겟 층은 CF 막으로부터 유도된 수소 할라이드(hydrogen halide)를 사용하여 에칭될 수 있는 임의의 재료(예를 들어, SiO2, TiO2)로 구성될 수 있다. 상기 에칭은 타겟 층을 구성하는 재료에 대해 높은 선택성을 가지므로, 예를 들어 실리콘 또는 금속 질화물 또는 탄화물로 구성된 막을 실질적으로 에칭하지 않고 실리콘 또는 금속 산화물로 구성된 막이 선택적으로 에칭될 수 있다. 일부 구현예에서, 타겟 층은, 적절한 에천트 막이 선택되는 한, 플루오린 이외의 할로겐을 사용하여 에칭될 수 있는 재료로 구성될 수 있다. 통상적으로, 에천트 막은 반응성 이온 에칭(RIE: reactive ion etching) 공정에서 산소 플라즈마에 노출된다. 에칭 공정이 자기 제한 반응 공정(또는 포화 공정)을 수반하기 때문에, 높은 제어성이 실현될 수 있다.
종래기술에 대해 달성된 본 발명의 양태 및 장점을 요약하기 위한 목적으로, 본 발명의 특정 목적 및 장점이 본 개시에서 설명된다. 물론, 모든 목적 및 장점이 본 발명의 임의의 특별한 구현예에 따라 반드시 달성되는 것이 아니라는 것을 이해하여야 한다. 따라서, 예들 들어 당업자는 본 발명이 본원에서 교시 또는 제안될 수 있는 다른 목적 또는 장점을 반드시 달성하지 않고, 본원에 교시된 바와 같은 하나의 장점 또는 여러 장점들을 달성 또는 최적화 하는 방식으로 구현되거나 수행될 수 있다는 것을 인식할 것이다.
본 발명의 다른 양태, 특징, 및 장점은 다음의 상세한 설명으로부터 명백해질 것이다.
본 발명의 이와 같은들 특징 및 다른 특징은 이제 바람직한 구현예의 도면을 참조하여 설명될 것이고, 이는 예시하기 위해 의도된 것이며 본 발명을 한정하기 위해 의도된 것은 아니다. 도면은 예시적인 목적으로 상당히 간략화되고, 반드시 일정한 비율로 도시되지 않는다.
도 1은 본 발명의 일 구현예에서 사용할 수 있는 플라즈마 보조 순환 에칭 장치의 개략도이다.
도 2는 본 발명의 일 구현예에 따른 한 사이클에서의 플라즈마 보조 순환 에칭의 개략적인 공정 시퀀스를 도시하며, 여기서 시퀀스에 예시된 단계는 ON 상태를 나타내는 반면, 시퀀스에 예시되지 않은 단계는 OFF 상태를 나타내며, 각각의 ON 및 OFF 상태의 길이는 각 공정의 지속시간을 나타내지 않는다.
도 3은 본 발명의 일 구현예에 따른 에칭 공정의 개략적인 도면을 예시하며, 여기서 (a)는 증착 단계를 나타내고, (b)는 프리 에칭(pre-etching) 단계를 나타내며, (c)는 에칭 단계를 나타낸다.
도 4는 본 발명의 일 구현예에 따른 원자층 에칭(ALE)을 도시하는 흐름도이다.
본 개시에서, "가스"는 기화된 고체 및/또는 액체를 포함할 수 있으며, 단일 가스 또는 가스 혼합물로 구성될 수 있다. 본 개시에서, 샤워 헤드를 통해 반응 챔버로 도입된 공정 가스는 에천트 가스 및 첨가성 가스로 구성되거나, 본질적으로 이루어지거나, 또는 이루어질 수 있다. 첨가성 가스는 통상적으로 에천트 가스를 희석시키고 여기 상태에 있을 때 에천트 가스와 반응하기 위한 희석 가스를 포함한다. 에천트 가스는 희가스(noble gas)와 같은 캐리어 가스와 함께 도입될 수 있다. 공정 가스 이외의 가스, 즉 샤워 헤드를 통과하지 않고 도입되는 가스는, 예를 들어 반응 공간을 밀봉하기 위해 사용될 수 있고, 희가스와 같은 밀봉 가스를 포함한다. 일부 구현예에서, 용어 "에천트 가스"는 일반적으로 기판 상의 타겟 층을 에칭하는 에칭 반응에 참여하는 적어도 하나의 기상 또는 기화 된 화합물을 지칭하며, 특히 여기된 상태에서 타겟 층 상에 증착되고 플라즈마에 의해 활성화될 때 타겟 층을 에칭하는 적어도 하나의 화합물을 지칭한다. 용어 "반응물 가스"는 에천트 막의 증착, 에천트 막의 활성화, 또는 에천트 막의 성분에 의한 에칭 반응을 촉매하는 적어도 하나의 기상 또는 기화된 화합물을 지칭한다. 반응물 가스는 퍼징 가스로서의 역할을 할 수 있다. 희석 가스 및/또는 캐리어 가스는 "반응물 가스"로서의 역할을 할 수 있다. 용어 "캐리어 가스"는 에천트 가스를 혼합된 상태에서 반응 공간으로 운반하고 에천트 가스를 포함하는 혼합된 가스로서 반응 공간에 진입하는 비-여기된 상태의 불활성(inert) 또는 비활성(inactive) 가스를 지칭한다.
또한, 본 개시에서, 실행 가능한 범위는 일상적인 작업에 기초하여 결정될 수 있으므로 변수의 임의의 두 수치가 변수의 실행 가능한 범위를 구성할 수 있고, 표시된 임의의 범위는 종점(endpoint)을 포함하거나 배제할 수 있다. 추가적으로, 표시된 변수의 임의의 값은 ("약"으로 표시되는지의 여부에 관계없이) 정확한 값 또는 대략적인 값을 지칭할 수 있고 등가물을 포함할 수 있으며, 일부 구현예에서는 평균, 중간, 대표, 다수 등을 지칭할 수 있다. 또한, 본 개시에서, 용어 "~의해 구성되는" 및 "갖는"은 일부 구현예에서 "통상적으로 또는 대략적으로 포함하는", "포함하는", "본질적으로 이루어지는", 또는 "이루어지는"을 독립적으로 지칭한다. 또한, 관사는 하나의 종 또는 다수의 종을 포함하는 하나의 속(genus)을 지칭한다. 본 개시에서, 임의의 정의된 의미는 일부 구현예에서 반드시 보통의 그리고 관례적인 의미를 배제하는 것은 아니다.
조건 및/또는 구조가 명시되지 않은 본 개시에서, 당업자는 일상적인 실험에 따라 본 개시의 관점으로 이와 같은 조건 및/또는 구조를 용이하게게 제공할 수 있다. 개시된 모든 구현예에서, 일 구현예에 사용된 임의의 요소는 이와 동등한 임의의 요소로 대체될 수 있으며, 의도된 목적을 위해 본원에 명시적으로, 반드시, 또는 본질적으로 개시된 것을 포함한다. 또한, 본 발명은 장치 및 방법에 동일하게 적용될 수 있다.
구현예는 바람직한 구현예에 대해 설명될 것이다. 그러나, 본 발명은 바람직한 구현예에 한정되지 않는다.
일부 구현예는 적어도 하나의 에칭 사이클을 포함하는 건식 에칭 공정에 의해 기판 상의 타겟 층을 에칭하는 방법을 제공하며, 여기서 에칭 사이클은 다음 단계를 포함한다: (i) 기판 상의 타겟 층 상에 반응성 종을 사용하여 카본 할라이드 막을 증착시키는 단계로서, 여기서 카본 할라이드 막 및 타겟 층은 서로 접촉하는, 단계; 및 (ii) (1) 타겟 층을 에칭하지 않는, 플라즈마만으로는 타겟 층을 실질적으로 에칭하지 않는, 비-할로겐 수소-함유 에칭 가스의 플라즈마를 사용하여 카본 할라이드 막을 에칭하고, 이에 의해 (2) 카본 할라이드 막과 타겟 층의 경계 영역에서 에천트 종으로서 수소 할라이드를 생성하여, 경계 영역 내의 타겟 층의 일부분을 에칭하는, 단계. 단계 (i)의 "반응성 종"은 타겟 층을 실질적으로 에칭하지 않고 타겟 층 상에 에천트 막을 형성한다. 본 개시에서, "실직적으로 제로(zero)"는 검출 가능한 양보다 적은 무형의 양, 타겟 또는 의도된 특성에 물질적으로 영향을 주지 않는 양, 또는 당업자에 의해 거의 제로로 인식되는 양, 예컨대, 10% 미만, 5% 미만, 1% 미만, 또는 일부 구현예에서 총합 또는 참조 값에 대한 이들의 임의의 범위를 지칭할 수 있다.
일부 구현예에서, 타겟 층은 실리콘 또는 금속 산화물로 구성되며, 여기서 금속은 SiO2, 금속 산화물(예를 들어, TiO2)과 같은 Ti, W, Ta 등일 수 있거나, 수소 할라이드 등으로 에칭할 수 있는 금속 단독일 수 있다. 에천트 가스가 Cl 또는 Br을 함유하는 경우, 타겟 층은 Al2O3, AlN, GaAs, GaN, GaP, InP 등으로 구성될 수 있다. 일부 구현예에서, 에천트 가스가 Cl을 함유하는 경우, 타겟 층은 폴리비닐 클로라이드로 구성될 수 있다. 당업자는 필요에 따라 일상적인 실험에 기초하여 에천트 가스 및 타겟 층의 가능한 조합을 결정할 수 있다. 일부 구현예에서, 타겟 층은, 플라즈마-강화 CVD, 열적 CVD, 순환 CVD, 플라즈마-강화 ALD, 열적 ALD, 라디칼 강화 ALD, 또는 임의의 다른 박막 증착 방법에 의해, 측벽 및 하단 표면, 및/또는 평평한 표면을 포함하는 트렌치 또는 비아(via)에 형성된다. 통상적으로, 타겟 층의 두께는 약 50 nm 내지 약 500 nm의 범위이다(원하는 막 두께는 막의 응용 및 목적 등에 따라 적절하다고 여겨지는 것으로 선택될 수 있음).
일부 구현예에서, 단계 (i)에서, 카본 할라이드 막은 기상 반응에 의해 증착되고, 반응성 종은 에천트 가스 또는 할로겐 및 탄소로 구성된 가스의 반응성 종이다. 일부 구현예에서, 할로겐은 F, Cl 또는 Br이다. 일부 구현예에서, 종래의 에천트 가스(예를 들어, "관련 기술"의 섹션에서 논의됨)를 포함하는 임의의 적절한 에천트 가스가 사용될 수 있다. 단계 (i)에서 에천트 가스는 타겟 층을 직접 에칭하는 반응성 에칭 가스로서의 역할을 하지 않지만 증착을 위한 가스로서의 역할을 하기 때문에, 바람직하게 에천트 가스는 이중 또는 삼중 결합을 갖는 CxFy이고, 여기서 x 또는 y는 정수이고, x는 적어도 2, 예를 들어, C2F2, C2F4, C3F6, C4F8, C5F8, C5F10 또는 이들의 임의의 조합이다. 이들 가스는 여기된 상태의 플루오로중합체를 용이하게 형성하는 경향이 있다. 단계 (i)에서, 에천트 가스는 타겟 층을 에칭하기보다는 에천트 막을 증착하기 위해 선택된다. 예를 들어, 산소 플라즈마가 실리콘 산화막 등을 에칭하기 위해 에천트 가스로부터 활성 에칭 종을 생성하기 때문에 산소-함유 가스가 사용되지 않는다. 일부 구현예에서, 반응물 가스는 Ar 및 He와 같은 희가스이다. 일부 구현예에서, 적절한 반응물 가스 및 다른 증착 조건을 선택함으로써, CF4, C2F6, C3F8, C4F10 등과 같은 실리콘 산화막을 에칭하는 데 통상적으로 사용되는 에천트 가스가 사용될 수 있다.
일부 구현예에서, 단계 (i)에서, 에천트 막을 증착시키기 위해 플루오린을 함유하는 것 이외의 에천트 가스가 사용될 수 있다. 예를 들어, C2H3Cl과 같은 알킬 할라이드가 사용될 수 있다. 또한, SF6, HCl, HBr 등은 CH4와 같은 하이드로카본과 조합하여 사용될 수 있다.
일부 구현예에서, 에천트 막은 원자층 증착(ALD : atomic layer deposition)과 같은 표면 반응에 의해 증착될 수 있고, 여기서 에천트 가스가 타겟 층의 표면 상에 화학 흡착된 후, 표면을 반응물 가스의 반응성 종에 노출시킨다.
일부 구현예에서, 단계 (i)는 플라즈마-강화 CVD인 가스상 반응을 사용한다. 일부 구현예에서, 플라즈마-강화 CVD는 다음 단계를 포함한다: (a) 기판이 배치된 반응 공간에 희가스를 연속적으로 공급하는 단계; (b) 반응 공간에 카본 할라이드 가스를 연속적으로 공급하는 단계; 및 (c) 희가스 및 카본 할라이드 가스를 여기시키지 않고 미리 설정된 지속시간 동안 (a) 및 (b) 단계를 거친 후, 반응 공간에 RF 전력을 인가하여 타겟 층 상에 카본 할라이드 막을 증착시키는 단계로서, 여기서 산화 가스는 단계 (ⅰ) 내지 (ⅲ)을 통해 반응 공간으로 공급되지 않는, 단계. 상기에서, 용어 "연속적으로"는 구현예에 따라 공간에서의 중단 없는(예를 들어, 기판을 통한 중단되지 않은 공급), 흐름에서의 중단 없는(예를 들어, 중단 없는 유입), 및/또는 일정한 속도인 것을 지칭한다(용어는 상기의 모든 것을 동시에 만족시킬 필요는 없음). 본 개시에서, "연속적인" 흐름은 일정한 유량을 가진다(대안적으로, 비록 흐름이 "연속적"일지라도, 유량은 시간에 따라 변할 수 있음). 일부 구현예에서, 단계 (c)의 지속시간은 단계 (a) 및 (b)의 미리 설정된 지속시간보다 짧다. RF 전력은 증착을 위해 짧은 시간 동안 반응 공간에 인가되기 때문에, RF 전력을 인가하기 전에 반응 공간을 카본 할라이드 가스로 완전히 충진하는 것이 중요하다.
일부 구현예에서, 단계 (i)는 카본 할라이드 막의 두께가 고평부 두께(또는 포화 두께)에 가까운 0.5 nm 내지 10 nm, 바람직하게는 1 nm 내지 5 nm의 범위 내에 있을 때까지 계속되고, 단계 (ii)에서 타겟 층의 에칭된 양은 카본 할라이드 막의 두께가 더 증가하더라도 증가하지 않는다.
일부 구현예에서, 단계 (i)의 지속시간은 타겟 층의 에칭된 부분의 두께가 고평부에 도달할 때까지 타겟 층의 에칭된 부분의 두께와 상호 관련되지만, 단계 (i)의 지속시간은 증가하며, 단계 (i)는 타겟 층의 에칭된 부분의 두께가 고평부에 도달하거나 또는 고평부 근처의 지점에 도달할 때까지 계속된다. 상기의 메커니즘은 본 발명을 한정하도록 의도되는 것은 아니지만, 본 개시에서는 메커니즘이 이전에 논의되었다.
일부 구현예에서, 단계 (ii)는 실질적으로 타겟 층의 경계 영역의 전체 부분이 에칭됨을 나타내는, 카본 할라이드 막이 실질적으로 완전히 에칭될 때까지 계속된다. 본 개시에서, "실직적으로 전체" 등은 무형의 양만큼, 검출 가능한 양만큼, 타켓 또는 의도된 특성에 물질적으로 영향을 주지 않는 양만큼, 또는 당업자에 의해 사소한 값으로 인식되는 양, 예컨대, 10% 미만, 5% 미만, 1% 미만, 또는 일부 구현예에서 총합 또는 참조 값에 대한 이들의 임의의 범위만큼 짧은 전체를 지칭할 수 있다. 바람직하게는, 단계 (ii)는 타겟 층의 경계 영역의 전체 부분이 완전히 제거되었음을 나타내는, 카본 할라이드 막이 완전히 에칭될 때까지 계속된다. 타겟 층의 "경계 영역"은 카본 할라이드 막이 완전히 에칭될 때 에칭되는 영역으로 정의된다. 카본 할라이드의 잔류물이 타겟 층의 표면 상에 잔류할 때, 잔류물은 타겟 층의 에칭과 적어도 부분적으로 간섭하여 타겟 층의 에칭된 깊이의 평면내 균일성에 영향을 줄 수 있다.
일부 구현예에서, 단계 (ii)에서, 타겟 층의 에칭된 부분의 두께는 0.1 nm 내지 2.0 nm, 바람직하게는 0.5 nm 내지 1.0 nm이며, 0.1 nm/사이클 미만인 원자층 에칭(ALE)에서 정의된 단일 층의 두께보다 두껍다.
일부 구현예에서, 단계 (ii)에서, 비-할로겐 수소-함유 에칭 가스는 수소 또는 암모니아 또는 수소 또는 암모니아와 희귀 가스(rare gas)의 혼합물이다. 일부 구현예에서, 수소-함유 에칭 가스는 산소를 함유하지 않는다. 그러나, 반응성 이온 에칭에 의해 타겟 층을 에칭하기 위해 에천트 막을 활성화시키도록 임의의 적절한 반응물 가스가 선택될 수 있다. 일부 구현예에서, Ar 및 He와 같은 희가스, 또는 질소 가스가 수소-함유 가스와 조합하여 반응물 가스로서 사용될 수 있다.
일부 구현예에서, 단계 (ii)에서, 반응성 이온 에칭(RIE)에 의해 카본 할라이드 막이 에칭된다. RIE는 유도-결합 플라즈마 에칭 또는 용량-결합 플라즈마 에칭일 수 있다. 일부 구현예에서, 용량 결합 플라즈마 에칭은 다음을 포함한다: (a) 기판이 배치된 반응 공간에 반응물 가스를 연속적으로 공급하는 단계; 및 (b) 반응물 가스를 여기시키지 않고 단계 (a)의 미리 설정된 지속시간의 경과 후, 반응 공간에 RF 전력을 인가하여 카본 할라이드 막 및 타겟 층을 에칭하는 단계.
일부 구현예에서, 단계 (i) 및 (ii)로 구성된 에칭 사이클은 타겟 층의 원하는 에칭된 깊이가 얻어 질 때까지 적어도 2회 반복된다. 에칭 사이클은 자기 제한 에칭 공정 또는 포화 공정이기 때문에, 타겟 층의 에칭된 깊이는 수행 된 사이클의 수에 비례한다.
일부 구현예에서, 단계 (i) 및 단계 (ii)는 동일 반응 챔버에서 연속적으로 수행된다. 상기에서, 단어 "연속적으로"는 다음 중 적어도 하나를 지칭한다: 진공을 파괴하지 않고, 대기에 노출되지 않고, 챔버를 개방하지 않고, 인-시츄(in-situ) 공정으로서, 연속적인 단계로서 중단 없이, 공정 조건의 변경 없이, 및 구현예에 따라 단계 사이의 기판 표면 상에 화학적 변화를 유발하지 않음. 일부 구현예에서, 퍼징 또는 문맥에서의 다른 무시할 수 있는 단계와 같은 보조 단계는 단계로 간주되지 않으며, 따라서 단어 "연속적으로"는 보조 단계에 개입하는 것을 배제하지 않는다.
일부 구현예는 도면을 참조하여 설명되지만, 본 발명을 한정하려는 것은 아니다.
도 3은 본 발명의 일 구현예에 따른 에칭 공정의 한 사이클의 개략적인 도면으로서, 여기서 (a)는 증착 단계를 나타내고, (b)는 프리 에칭 단계를 나타내며, (c)는 에칭 단계를 나타낸다. 증착 단계(단계 (a)) 이전에, 타겟 층(42)이 형성되는 기판(41)(예를 들어, 실리콘 웨이퍼 또는 다른 반도체 웨이퍼)이 반응 공간에 제공된다. 증착 단계에서, 타겟 층(42) 상에는 포화 두께(T1) 이상의 두께로 카본 할라이드 막(에천트 막) (43)이 증착되고, 카본 할라이드 막(43) 및 타겟 층 (42)은 서로 접촉한다. 포화 두께(T1)는, 에천트 막의 두께가 포화 두께 (T1)를 초과하여 더 증가하더라도, 타겟 층의 에칭에 기여하지 않는 부분, 즉 타겟 층의 에칭 양이 증가하지 않는 두께로서 정의된다. 프리 에칭 단계(단계 (b))에서, 에천트 막(43)은 수소 플라즈마(수소 라디칼 H*)와 같은 플라즈마에 노출되어, 에천트 막을 에칭하고, 하이드로카본 가스 및 수소 할라이드 등과 같은 가스 성분을 생성하며, 예를 들어 다음의 화학 반응(에천트 막이 CxFy에 의해 구성되고 x 및 y가 정수인 경우)을 통해 포화 두께(T1) 이상으로 에천트 막(43)의 상단 부분을 제거한다:
CxFy + (4x + y) H*
Figure pat00001
xCH4 + yHF (1)
상기 반응은 일반적인 반응이며, 플루오로카본의 조성물은 증착 방법, 에천트 가스의 유형 등에 따라 달라지므로 간략화된다. 또한, CH4 이외의 하이드로카본이 생성될 수 있지만, 이와 같은 하이드로카본은 최종적으로 CH4로 분해되기 쉽기 때문에, 반응은 CH4로 나타낼 수 있다. 반응 (1)을 통해, 수소 라디칼에 의해, HF 성분을 생성하면서 에천트 막으로부터 탄소 성분이 제거될 수 있으며, 이어서 SiO2 막을 에칭할 수 있다.
에천트 막(43)의 에칭이 진행되고, 에천트 막(43)이 포화 두께(T1)까지 에칭되면, 에천트 막(43)으로부터 HF 등과 같은 가스 성분이 경계 영역(44)에서 HF 가스를 사용하여 깊이(T2)를 갖는 타겟 층(42)의 일부분으로부터 SiF4, 2H2O 등과 같은 가스 성분을 동시에 생성한다:
SiO2 + 4HF
Figure pat00002
SiF4 + 2H2O (2)
반응 (2)를 통해, SiO2 막이 에칭되고, 여기서, 생성된 H2O는 에칭 반응을 추가로 보조할 수 있다. 이 에칭은 화학적 에칭이므로, 에칭 선택성이, 예를 들어 SiO2와 SiN 사이에서 현저하게 높고(SiO2에 대한 에칭률은 높지만 SiN에 대한 에칭률은 실질적으로 없음), 컨포멀(conformal) 에칭(균일한 에칭)이 수행될 수 있다. 이들 특징은 종래의 에칭 방법으로 달성될 수 없다.
경계 영역(44)은 포화 두께(T1)를 갖는 에천트 막(43)의 경계 영역 및 깊이(T2)를 갖는 타겟 층(42)의 경계 영역으로 구성된다. 경계 영역의 총 두께(T1 + T2)는, 예를 들어 RF 전력 및 반응 공간의 압력에 따라 플라즈마 내의 이온 에너지에 의존할 수 있다. 경계 영역(44)은 SiCOF와 같은 혼합된 성분으로 구성된 중간체로 구성될 수 있다. 반응 (1) 및 (2)에 도시된 바와 같이, 프리 에칭 단계(단계 (b))는 두 단계로 구성되며, 여기서 제1 단계는 에천트 막(예를 들어, 카본 할라이드 막)을 에칭하고 수소 라디칼에 의해 에천트 종(예를 들어, 수소 할라이드)을 생성하며, 제2 단계는 에천트 종에 의해 타겟 층을 에칭한다. 제2 단계는 플라즈마 없이(RF 전력을 인가하지 않고) 수행될 수 있는 반면, 제1 단계는 플라즈마를 사용한다. 그러나, 제1 및 제2 단계는 서로 중첩하는데, 즉 에천트 종에 의해 타겟 층을 에칭하는 제2 단계는 제1 단계의 종료 전에 시작된다.
에칭 단계(단계 (c))에서, 경계 영역 또는 중간 층(44)은 가스 성분으로서 제거되고, 여기서 타겟 층(42)은 깊이(T2)만큼 에칭되어 에칭된 타겟 층(45)을 얻는다. 단계 (b) 및 (c)가 단계의 원리를 용이하게 이해할 수 있도록 개별적으로 도시되어 있지만, 이들 단계가 동시에 발생한다는 것을 유의해야 한다. 플라즈마만으로는 타겟 층을 실질적으로 에칭하지 않기 때문에, 타겟 층(45)의 에칭은 경계 영역(44)이 제거될 때 정지된다.
일부 구현예에서, 공정은 원자층 에칭(ALE)의 흐름도를 도시하는 도 4에 도시된 바와 같이 수행될 수 있다. 단계 (a)에서, CF 막은 바람직하게 플라즈마-강화 또는 열적 CVD 또는 컨포멀 증착(예를 들어, 헥사플루오로프로필렌 옥사이드(HFPO) 열적 증착)을 수행할 수 있는 임의의 적합한 방법에 의해 증착된다. 단계 (b)(반응 공간을 퍼징) 후에, 단계 (c)에서, CF 막은 수소 플라즈마에 노출되어, 타겟 층(예를 들어, SiO2)의 표면에서 HF를 생성시킨다. 이 공정에서, 수소 라디칼의 존재가 충분할 수 있거나 또는 추가적으로, 이온 충격이 일부 구현예에서 필요할 수 있다. 단계 (c) 이후에, 반응 공간은 단계 (d)에서 퍼지된다. 단계 (a) 내지 (d)는 타겟 층의 원하는 두께가 에칭될 때까지 여러 번 반복될 수 있는 ALE의 한 사이클을 구성한다. 에천트 막(CF 막)이 수소 플라즈마에 노출되어 에칭되고, 타겟 층이 수소 플라즈마에 노출되지 않기 때문에, 타겟 층에는 플라즈마 손상이 적게 또는 실질적으로 유발되지 않는다.
일부 구현예에서, 공정 시퀀스는 도 2에 예시된 바와 같이 설정될 수 있다. 도 2는 본 발명의 일 구현예에 따른 한 사이클에서 플라즈마-보조 순환 에칭의 개략적인 공정 시퀀스를 도시하며, 여기서 시퀀스에서 예시된 단계는 ON 상태를 나타내는 반면, 시퀀스에 예시되지 않은 단계는 OFF 상태를 나타내며, 각 ON 및 OFF 상태의 길이가 각 공정의 지속시간을 나타내는 것은 아니다. 이와 같은 구현예에서, 한 에칭 사이클은 증착 단계(이와 같은 구현예에서 플라즈마-강화 CVD) 및 에칭 단계를 포함한다. 증착 단계는 "단계 1"을 포함하고, 에칭 단계는 "퍼지 1", "단계 2", "단계 3", 및 "퍼지 2"를 포함한다.
플라즈마-강화 CVD 단계인 증착 단계의 "단계 1"에서, Ar 및/또는 He와 같은 희석 가스는 기판이 배치된 반응 공간으로 연속적으로 공급되고, 반면에 카본 할라이드 가스는 수소 가스가 공급되지 않고 반응 공간에 RF 전력을 연속적으로 인가하는 동안 연속적으로 반응 공간에 공급된다. 증착 단계의 "단계 1"에 있어서, 원하는 두께(예를 들어, 0.5 ㎚ 내지 10 ㎚, 통상적으로는 약 2 ㎚)의 할로겐-함유 막(예를 들어, 카본 할라이드 막)이 타겟 층 상에 에천트 막으로서 증착된다. 단계 1은 에천트 막의 증착 단계(핀홀없이 두께 방향에 수직인 방향으로 연장되고, 타겟 층의 관련 구역을 전체적으로 커버하는 단계)이고, 이 단계는 타겟 층 상에 반응성 사이트를 제공하는 단계 이상의 의미를 갖는다. 증착 단계는 열적 CVD, PVD, PEALD 등의 임의의 적합한 증착 단계일 수 있으며, 당업자는 이에 따라 "단계 1"을 용이하게 수정할 수 있다.
"단계 1" 후에, 희석 가스 및 카본 할라이드 가스를 공급하지 않고, RF 전력을 인가하지 않고, 수소 가스(에칭 가스)를 연속적으로 반응 공간에 공급하는 에칭 단계의 "퍼지 1"을 개시한다. 에칭 가스는 암모니아와 같은 수소를 함유하는 가스 또는 수소-함유 가스와 희귀 가스(예를 들어, Ar, He)의 혼합물일 수 있다. "퍼지 1"은 반응되지 않은(non-reacted) 생성물, 원하지 않는 부산물 및 임의의 잔류하는 증착 가스(들)를 제거하고 반응 공간을 안정화하고 에칭 준비를 하기 위한 것이다. "퍼지 1"의 미리 설정된 지속시간이 경과한 후, "단계 2"에서, 할로겐-함유 가스를 공급하지 않고 수소 가스(에칭 가스)를 공급하여 수소 라디칼을 생성하고, 이어서 카본 할라이드와 같은 에천트 막과의 반응의 결과로서 수소 할라이드와 같은 에천트 종을 생성하는 동안, RF 전력이 반응 공간에 인가되어 할로겐-함유 막(에천트 막, 예를 들어, 카본 할라이드 막)과 타겟 층을 에칭한다. 수소 할라이드와 같은 에천트 종은 타겟 층과 할로겐-함유 막 사이의 경계 영역에서 에천트 종과 접촉하는 타겟 층 표면을 화학적으로 에칭한다. "단계 2"에서, 타겟 층의 화학적 에칭은 수소 할라이드와 같은 에천트 종이 생성됨에 따라 시작되고 진행되며, 수소 가스 흐름 및 RF 전력의 인가가 정지되는 "단계 3"에서, 일부 에 천트 종이 잔류하기 때문에, 잔류 에천트 종이 소비되거나 "퍼지 2"가 시작될 때까지 잔류 에천트 종은 타겟 층 표면을 계속 에칭한다. 수소 라디칼을 생성하기 위한 적절한 수단은 "단계 2"에서 사용될 수 있다. "단계 2"의 지속시간은 할로겐-함유 막의 두께 등에 따라 결정될 수 있다. "단계 2"에서, 할로겐-함유 막은 전체적으로 에칭되거나 제거된다. "단계 3"의 지속시간은 "단계 2"의 끝에서 잔류 수소 할라이드가 얼마나 남았는지와 얼마나 많은 타겟 층 표면을 에칭해야 하는지 등에 따라 결정될 수 있다. "퍼지 3"에서, 희석 가스를 공급함으로써 반응되지 않은 생성물, 원하지 않는 부산물 및 임의의 잔류하는 에천트 종을 제거하기 위해 반응 공간을 퍼지한다. 이 에칭 사이클은 타겟 층의 원하는 깊이가 에칭될 때까지 반복될 수 있다.
"단계 2"에서, 수소 라디칼을 함유하는 수소 플라즈마를 생성하기 위해 RF 전력이 사용되므로, 대안적으로 리모트 플라즈마 유닛을 사용함으로써, 예를 들어 수소 라디칼을 함유하는 수소 플라즈마가 또한 생성될 수 있다. 일부 구현예에서, RF 전력은 펄스로 인가된다.
일부 구현예에서, 에칭 사이클은 아래의 표 1에 나타낸 조건 하에서 수행될 수 있다.
[표 1](수치는 근사치임)
Figure pat00003
도 2에 예시된 시퀀스에서, 할로겐-함유 가스는, 특히 할로겐 함유 가스가 C5F8, C5F10 등과 같은 액체 재료의 기화된 가스인 경우, 반응 공간에 연속적으로 공급될 수 있는 캐리어 가스를 사용하여 공급될 수 있다. 이는 플로우-패스 스위칭(FPS: flow-pass switching)(예를 들어, 2015년 8월 18일자로 출원된 미국 특허출원 제14/829,565호에 개시된 시스템, 그 개시 내용은 그 전체가 참조로 포함됨)을 이용하여 달성될 수 있고, 여기서 캐리어 가스 라인은 전구체 저장소(보틀)를 갖는 우회(detour) 라인을 구비하고, 메인 라인 및 우회 라인이 스위칭되고, 캐리어 가스만을 반응 챔버에 공급하도록 의도될 때는 우회 라인이 폐쇄되는 반면, 캐리어 가스와 전구체 가스 둘 모두를 반응 챔버에 공급하도록 의도될 때는 메인 라인이 폐쇄되어, 캐리어 가스는 우회 라인을 통해 흐르고 전구체 가스와 함께 보틀로부터 흐른다. 이와 같은 방식으로, 캐리어 가스는 반응 챔버 내로 연속해서 흐를 수 있고, 메인 라인과 우회 라인을 스위칭함으로써 전구체 가스를 펄스로 운반할 수 있다.
일부 구현예에서, 타겟 층은 Si 단독, 금속 단독, 상기의 산화물, 또는 상기의 카보네이트로 구성되며, 이에 따라 적절한 에천트 가스(할로겐-함유 가스)가 선택될 수 있어 에천트 막(할로겐-함유 막)을 형성할 수 있고, 이어서 수소 라디칼에 의해 에칭될 때 에천트 종을 생성한다. 예를 들어, 타겟 층이 SiO2로 구성되는 경우, 에천트 가스는 F를 할로겐으로서 적절하게 함유하고, 반면 타겟 층이 Si로 구성되는 경우, 에천트 가스는 Cl을 할로겐으로서 적절하게 함유한다. 당업자는 본 개시 내용 및 일상적인 실험을 통해 타겟 층에 적절한 에천트 가스를 용이하게 선택할 수 있다. 아래의 표 2는 실시예를 나타낸다. 에천트 종에 의한 에칭 공정은 높은 선택성을 갖기 때문에, 예를 들어 실리콘 질화물을 유지하면서 실리콘 산화물만을 선택적으로 에칭할 수 있다. 에천트 막은 수소 라디칼에 의해 수소 할라이드와 같은 에천트 종을 생성하도록 분해될 수 있는 카본 할라이드로 구성될 수 있다. 수소 라디칼은 수소를 함유하는 에천트 가스 또는 수소-함유 가스와 희귀 가스의 혼합물로부터 생성될 수 있다.
[표 2](적절한 조합)
Figure pat00004
공정 사이클은, 예를 들어 도 1a에 예시된 장치를 포함하는 임의의 적절한 장치를 사용하여 수행될 수 있다. 도 1은 본 발명의 일부 구현예에 사용될 수 있고, 바람직하게는 아래에 설명되는 시퀀스를 수행하기 위해 프로그래밍된 제어와 협력하는 플라즈마 보조 순환 에칭 장치의 개략도이다. 이 도면에서, 서로 마주하며 평행한 한 쌍의 전기적 전도성 평판 전극(4, 2)을 반응 챔버(3)의 내부(반응 구역)(11)에 제공하고, HRF 전력(13.56 MHz 또는 27 MHz)(20)을 일 측부에 인가하고 다른 측부(12)를 전기적으로 접지시킴으로써, 플라즈마가 전극 사이에서 여기된다. 온도 조절기가 하부 스테이지(하부 전극)(2)에 제공되고, 그 위에 배치된 기판(1)의 온도는 주어진 온도로 일정하게 유지된다. 상부 전극(4)은 샤워 판(shower plate)로서의 역할도 수행하며, 희가스, 반응물 가스 및 에천트 가스가 각각의 가스 라인(21, 22 및 23)을 통해서 그리고 샤워 플레이트(4)를 통해서 반응 챔버(3)로 도입된다. 추가적으로, 반응 챔버(3)에는 배기 라인(7)을 갖는 원형 덕트(13)가 제공되고, 이를 통해 반응 챔버(3)의 내부(11)에 있는 가스가 배기된다. 추가적으로, 희석 가스가 가스 라인(23)을 통해 반응 챔버(3)로 도입된다. 또한, 반응 챔버(3) 아래에 배치된 이송 챔버(5)는, 이송 챔버(5)의 내부(이송 구역)(16)를 통해 반응 챔버(3)의 내부(11)로 밀봉 가스를 도입하기 위한 밀봉 가스 라인(24)을 구비하며, 여기서 반응 구역과 이송 구역을 분리하기 위한 분리 판(14)이 제공된다(웨이퍼가 이송 챔버(5)로 또는 이송 챔버(5)로부터 이송되는 게이트 밸브는 이 도면에서 생략됨). 이송 챔버는 또한 배기 라인(6)을 구비한다. 일부 구현예에서, 다중-요소 막의 증착 및 표면 처리는 동일한 반응 공간에서 수행되어, 모든 단계들이 기판을 공기 또는 다른 산소-함유 대기에 노출시키지 않고 연속적으로 수행될 수 있다. 일부 구현예에서, 가스를 여기시키기 위해 리모트 플라즈마 유닛이 사용될 수 있다.
일부 구현예에서, 듀얼 챔버 반응기(서로 근접하게 배치된 웨이퍼를 프로세싱하기 위한 2개의 섹션 또는 컴파트먼트)가 사용될 수 있고, 반응물 가스 및 희가스는 공유된 라인을 통해 공급될 수 있고, 반면 전구체 가스는 공유되지 않은 라인을 통해 공급된다. 일부 구현예에서, 증착 단계는 에칭 단계와 상이한 장치를 사용하여 수행될 수 있다.
당업자는 프로그래밍된, 그렇지 않으면 증착 및 본원의 다른 곳에서 설명되는 반응기 세척 공정이 유발되도록 구성된, 하나 이상의 제어기(들)가 장치에 포함된다는 것을 이해할 것이다. 제어기(들)는, 당업자가 이해하는 바와 같이, 다양한 전력원, 가열 시스템, 펌프, 로보틱스, 및 반응기의 가스 흐름 제어기 또는 밸브와 연통한다.
아래의 작용 실시예를 참조하여 본 발명이 더 설명된다. 그러나, 이와 같은 실시예는 본 발명을 한정하도록 의도된 것은 아니다. 조건 및/또는 구조가 명시되지 않는 본 실시예에서, 당업자는 일상적인 실험의 상황에 따라 본 개시의 관점으로 이와 같은 조건 및/또는 구조를 용이하게 제공할 수 있다. 또한, 특정한 실시예에 적용된 수치는 일부 구현예에서 적어도 ±50%의 범위로 수정될 수 있으며, 이와 같은 수치는 근사치이다.
실시예
실시예 1(예언적 실시예 )
300 mm 기판 상에 타겟 층으로서 PEALD 또는 PECVD에 의해 실리콘 산화막, 실리콘 질화막, 및 실리콘 카바이드 막이 각각 약 20 nm의 두께로 형성된다. 에천트 막(CF 막)의 증착 및 각 타겟 층의 에칭은 도 1에 예시된 플라즈마 보조 에칭 장치를 사용하여 아래의 [표 3]에 나타낸 조건 하에서 수행된다. 각 에칭 사이클에서 사용된 시퀀스는 도 2에 도시되어 있다.
[표 3](수치는 근사치임)
Figure pat00005
증착 단계 및 에칭 단계를 포함하는 에칭 사이클은 각 기판에 대해 3 및 6회 반복된다. 에칭 사이클 후에, 각각의 타겟 층의 두께는 타원편광법(ellipsometry)에 의해 측정된다. 그 결과, SiO2 막의 사이클 당 에칭률(EPC: etching rate per cycle)은 약 0.7 nm/사이클 이었지만, SiN 막 및 SiC 막의 에칭률은 거의 제로, 즉 막 두께의 감소가 실질적으로 없었다.
당업자는 본 발명의 사상을 벗어나지 않고, 다수의 그리고 다양한 변형이 이루어질 수 있음을 이해할 것이다. 따라서, 본 발명의 형태는 단지 예시적인 것이며 본 발명의 범위를 한정하도록 의도된 것이 아니라는 것을 분명히 이해해야 한다.

Claims (19)

  1. 적어도 하나의 에칭 사이클을 포함하는 건식 에칭 공정에 의해 기판 상의 타겟 층을 에칭하는 방법으로서, 에칭 사이클은:
    (i) 기판 상의 타겟 층 상에 반응성 종을 사용하여 카본 할라이드 막을 증착시키는 단계로서, 상기 카본 할라이드 막 및 타겟 층은 서로 접촉하는, 단계; 및
    (ii) (1) 타겟 층을 에칭하지 않는, 플라즈마만으로는 타겟 층을 실질적으로 에칭하지 않는, 비-할로겐 수소-함유 에칭 가스의 플라즈마를 사용하여 카본 할라이드 막을 에칭하고, 이에 의해 (2) 카본 할라이드 막과 타겟 층의 경계 영역에서 에천트 종으로서 수소 할라이드를 생성하여, 경계 영역 내의 타겟 층의 일부를 에칭하는 단계를 포함하는, 방법.
  2. 제1항에 있어서, 상기 단계 (ii)는 타겟 층의 경계 영역의 실질적으로 전체 부분이 에칭되는 것을 표시하는, 카본 할라이드 막이 실질적으로 완전히 에칭될 때까지 계속되는, 방법.
  3. 제1항에 있어서, 단계 (i)의 지속시간은 타겟 층의 에칭된 부분의 두께가 고평부에 도달할 때까지 타겟 층의 에칭된 부분의 두께와 상호 관련되고, 반면 단계 (i)의 지속시간은 증가하며, 단계 (i)는 타겟 층의 에칭된 부분의 두께가 고평부에 도달하거나 또는 고평부 근처의 지점에 도달할 때까지 계속되는, 방법.
  4. 제1항에 있어서, 상기 에칭 사이클은 적어도 2회 반복되는, 방법.
  5. 제1항에 있어서, 상기 단계 (i)는 카본 할라이드 막의 두께가 0.5 nm 내지 10 nm의 범위 내에 있을 때까지 계속되는, 방법.
  6. 제1항에 있어서, 상기 단계 (ii)에서, 타겟 층의 에칭된 부분의 두께는 0.1 nm 내지 2.0 nm인, 방법.
  7. 제1항에 있어서, 상기 단계 (i)에서, 카본 할라이드 막은 기상 반응에 의해 증착되고, 상기 반응성 종은 에천트 가스 또는 할로겐 및 탄소로 구성된 가스인, 방법.
  8. 제7항에 있어서, 할로겐은 F 또는 Cl인, 방법.
  9. 제8항에 있어서, 할로겐은 F이고, 에천트 종은 HF인, 방법.
  10. 제8항에 있어서, 상기 에천트 가스는 x 및 y가 정수이고 x가 적어도 2인 이중 또는 삼중 결합을 갖는 CxFy인, 방법.
  11. 제7항에 있어서, 기상 반응은 플라즈마-강화 CVD인, 방법.
  12. 제11항에 있어서, 상기 플라즈마-강화 CVD는:
    (a) 기판이 배치된 반응 공간에 희가스를 연속적으로 공급하는 단계;
    (b) 반응 공간에 카본 할라이드 가스를 연속적으로 공급하는 단계; 및
    (c) 희가스 및 카본 할라이드 가스를 여기시키지 않고 미리 설정된 지속시간 동안 (a) 및 (b) 단계를 거친 후, 반응 공간에 RF 전력을 인가하여 타겟 층 상에 카본 할라이드 막을 증착시키는 단계로서, 상기 산화 가스가 단계 (a) 내지 (c)을 통해 반응 공간으로 공급되지 않는 단계를 포함하는, 방법.
  13. 제12항에 있어서, 상기 단계 (c)의 지속시간은 단계 (a) 및 (b)의 미리 설정된 지속시간보다 짧은, 방법.
  14. 제1항에 있어서, 단계 (ii)에서, 비-할로겐 수소-함유 에칭 가스는 수소 또는 암모니아 또는 수소 또는 암모니아와 희귀 가스의 혼합물이며 산소를 함유하지 않는, 방법.
  15. 제1항에 있어서, 단계 (ii)에서, 카본 할라이드 막이 반응성 이온 에칭(RIE)에 의해 에칭되는, 방법.
  16. 제15항에 있어서, 상기 RIE는 용량 결합 플라즈마 에칭인, 방법.
  17. 제16항에 있어서, 용량 결합 플라즈마 에칭은:
    (a) 기판이 배치된 반응 공간에 반응물 가스를 연속적으로 공급하는 단계; 및
    (b) 반응물 가스를 여기시키지 않고 단계 (a)의 미리 설정된 지속시간의 경과 후, 반응 공간에 RF 전력을 인가하여 카본 할라이드 막 및 타겟 층을 에칭하는 단계를 포함하는, 방법.
  18. 제1항에 있어서, 상기 타겟 층은 SiO2, 금속 산화물, 또는 수소 할라이드에 의해 에칭 가능한 금속으로 구성되는, 방법.
  19. 제1항에 있어서, 상기 단계 (i) 및 단계 (ii)는 동일한 반응 챔버에서 연속적으로 수행되는, 방법.
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