KR20190012097A - 부바이어스를 사용하는 peald로 막을 증착하는 방법 - Google Patents

부바이어스를 사용하는 peald로 막을 증착하는 방법 Download PDF

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KR20190012097A
KR20190012097A KR1020180068182A KR20180068182A KR20190012097A KR 20190012097 A KR20190012097 A KR 20190012097A KR 1020180068182 A KR1020180068182 A KR 1020180068182A KR 20180068182 A KR20180068182 A KR 20180068182A KR 20190012097 A KR20190012097 A KR 20190012097A
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film
bias voltage
deposition cycles
electrode
plasma
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KR102691272B1 (ko
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도시야 스즈키
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에이에스엠 아이피 홀딩 비.브이.
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Abstract

기판 상에 PEALD에 의해 막을 형성하는 방법은 증착 사이클들을 포함하고, 각 증착 사이클은, (i) 전구체를 상기 반응 공간에 펄스로 공급하여 상기 기판의 표면 상에 상기 전구체를 흡착시키는 단계; (ii)단계 (i) 후에, 상기 제2 전극에 RF 전력을 인가하여 상기 반응 공간에 상기 전구체가 흡착된 기판이 노출되는 플라즈마를 발생시켜서 상기 표면 상에 서브층을 형성하는 단계; 및 (iii) 단계 (ii)에서 RF 전력을 인가하는 동안 상기 제2 전극에 바이어스 전압을 인가하는 단계로서, 상기 바이어스 전압은 상기 제1 전극의 표면 위의 전위에 대하여 부(negative)이고, 상기 사이클은 다수의 서브층으로 구성되는 막이 원하는 두께를 가질 때까지 상기 다수의 서브층을 증착하기 위해 반복되는, 단계를 포함한다.

Description

부바이어스를 사용하는 PEALD로 막을 증착하는 방법{METHOD OF DEPOSITING FILM BY PEALD USING NEGATIVE BIAS}
본 발명은 일반적으로 부바이어스 전압에 의해 바뀌어진 용량 결합식 플라즈마(CCP)를 사용하는 플라즈마 강화 원자층 증착(PEALD)에 의해 기판 상에 막을 형성하는 방법에 관한 것이다.
플라즈마 강화 원자층 증착(PEALD)에 의해 증착되는 유전체막이 약 10의 단차비를 갖는 트렌치에 증착될 때, 등각성이 매우 높기(예컨대, 100%) 때문에, 이 유전체막은 반도체 제조 산업에서 널리 사용된다. 그러나, 용량 결합식 플라즈마(CCP)를 사용하는 종래의 PEALD는 다음의 단점들을 가진다. 플라즈마는 결국 총 전하가 거의 없게 되는 비율로 양이온과 자유전자들을 포함하는 이온화된 가스로서, CCP를 사용하는 PEALD에서, 막 형성은 이온들 및 라디칼을 사용하여 이루어진다. 이온 충돌은 막 성장 및 막 품질을 위해 중요하다. 그러나, 기판 표면에 가해지는 강한 이온 충돌은 문제들을 야기한다. 즉, 많은 PEALD 공정에서, 이온 충돌은 막 성질들을 악화시킨다. 도 5는 막의 증착에서 강한 이온 충돌(45)에 의해 야기되는 문제점들을 도시하는 데, 여기서 (a)는 증착된 막(42)과 기판(41) 사이의 결합의 끊어짐을 보여주고, (b)는 증착된 막(42)과 기판(41) 사이의 계면을 따라 기포(43a)의 형성(기포(43a)는 증착된 막의 표면 상에도 형성됨)을 보여주고, (c)는 증착된 막(42)과 기판(41) 사이에 증착된 하부층(44)의 손상 또는 식각을 보여준다.
플라즈마 출력을 감소시키고/감소시키거나 공정 압력을 증가시킴으로써 강한 이온 충돌의 역효과를 줄이는 것이 가능할 수 있다. 그러나, 플라즈마 출력이 감소되면, 플라즈마 밀도가 감소하여, 고르지 않거나 불균일한 플라즈마 분포가 생기게 되고, 공정 압력이 증가하면, 플라즈마의 점화가 어렵고 불안정하게 된다.
위에서 논의된 문제점들에 비추어, 본 발명자들은 적어도 일부 구현예들이 위에서 논의된 문제점들 중 일부 또는 전부를 효과적으로 해결할 수 있는 본 발명을 완성하였다.
위에서 논의된 문제점들을 비롯하여 종래 기술과 연관된 문제 및 해결책에 대한 임의의 논의는 단지 본 발명에 대한 맥락을 제공하기 위해서만 본 개시에 포함되었고, 그 논의의 일부 또는 전부가 본 발명이 이루어진 당시에 알려졌다는 것을 인정하는 것으로 받아들여져서는 안된다.
일부 구현예들은 서로 마주보는 용량 결합성 제1 및 제2 전극에 의해 정의된 반응 공간에서 플라즈마 강화 원자층 증착(PEALD)에 의해 기판 상에 막을 형성하는 방법을 제공하고, 여기서 상기 기판은 상기 제2 전극과 마주보는 상기 제1 전극 위에 놓이고, 상기 PEALD는 증착 사이클들을 포함하며, 상기 증착 사이클들 각각은 다음 단계들을 포함한다: (i) 전구체를 상기 반응 공간에 펄스로 공급하여 상기 기판의 표면 상에 상기 전구체를 흡착시키는 단계; (ii)단계 (i) 후에, 상기 제2 전극에 RF 전력을 인가하여 상기 반응 공간에 상기 전구체가 흡착된 기판이 노출되는 플라즈마를 발생시켜서 상기 표면 상에 서브층을 형성하는 단계; 및 (iii) 단계 (ii)에서 RF 전력을 인가하는 동안 상기 제2 전극에 바이어스 전압을 인가하는 단계로서, 상기 바이어스 전압은 상기 제1 전극의 표면 위의 전위에 대하여 부(negative)이고, 상기 사이클은 다수의 서브층으로 구성되는 막이 원하는 두께를 가질 때까지 상기 다수의 서브층을 증착하기 위해 반복되는, 단계. 상기 방법은 낮은 에너지를 가진 고밀도 플라즈마를 발생시키기 위해 최소한으로 개량된 임의의 종래 장치를 포함하는 임의의 적합한 CCP형 PEALD 장치를 사용하여 수행될 수 있다. 일부 구현예들은 다음 특징들을 특징으로 할 수 있다: (1) 더 낮은 플라즈마 전위를 갖는 더 낮은 이온 에너지 공정; (2) 더 높은 플라즈마 밀도를 갖는 더 높은 처리량; 및 (3) 상부 전극 위에서 더 작은 파티클 발생. 특히, 기판이 놓이는 하부 영역에서 이온 에너지 제어 능력에 주목할 만하다. 도 5와 관련하여 위에서 논의된 바와 같이, 이온 충돌은 층간 분리, 기포 발생, 또는 식각과 같은 결함들을 유도할 수 있고, PEALD 막 성질들을 악화시킬 수 있지만, 일부 구현예들은 이들 문제들을 효과적으로 제거하고, 특히 이온 충돌에 민감한 PEALD 공정에 특히 이점이 있어서, 양호한 막 성질들을 갖는 막 형성을 달성한다.
종래 기술을 넘어 달성된 본 발명의 양태 및 장점들을 요약하기 위한 목적으로, 본 발명의 특정 목적 및 장점들이 본 개시에 설명된다. 물론, 모든 목적 및 장점들이 본 발명의 임의의 특별한 구현예에 따라 반드시 달성되는 것이 아니라는 것을 이해하여야 한다. 따라서, 예들 들면 당업자는 본 발명이 본원에 교시 또는 제시될 수 있는 다른 목적들 또는 장점들을 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 또 다른 양태, 특성, 및 장점들은 다음의 상세한 설명으로부터 명확해 질 것이다.
본 발명의 이러한 그리고 기타 특징들은 바람직한 구현예의 도면을 참조하여 설명될 것이고, 이는 예시를 위해 의도된 것이며 본 발명을 한정하기 위함은 아니다. 도면은 예시의 목적으로 상당히 간략화되고, 반드시 스케일에 맞추어진 것은 아니다.
도 1은 본 발명의 구현예에 따라 부바이어스 전압을 갖는 단일 주파수 RF 전력을 사용하여 유전체 막을 증착하기 위한 PEALD(plasma-enhanced atomic layer deposition)의 개략적인 묘사이다.
도 2는 본 발명의 구현예에 따라 부바이어스 전압을 갖는 이중 주파수 RF 전력을 사용하여 유전체 막을 증착하기 위한 PEALD(plasma-enhanced atomic layer deposition)의 개략적인 묘사이다.
도 3은 본 발명의 구현예에 따라 바이어스 전압을 결정하기 위한 전위를 구성하는 성분들에 포함된 직류 성분을 측정하기 위한 전류의 개략적인 묘사이다.
도 4는 본 발명의 구현예에 사용할 수 있는 유동-통과 시스템(flow-pass system, FPS)을 이용한 전구체 공급 시스템의 개략적인 묘사를 도시하고, (b)는 전구체 없는 가스 유동을 도시한다.
도 5는 막의 증착에서 강한 이온 충돌에 의해 야기되는 문제점들을 도시하는 데, 여기서 (a)는 증착된 막과 기판 사이의 결합의 끊어짐을 보여주고, (b)는 증착된 막과 기판 사이의 계면을 따라 기포의 형성을 보여주고, (c)는 증착된 막과 기판 사이에 증착된 하부층의 손상 또는 식각을 보여준다.
도 6은 DC 바이어스 전압이 (a)에서 공정 사이클의 진행에 따라 변하고, 즉 (b)에서 이온 에너지가 공정 사이클의 진행에 따라 변하는 구현예를 도시한다.
도 7은 구현예를 도시하는 데, (a)는 부의 DC 바이어스 전압이 상부 전극에 인가될 때("w/DC bias")와 부의 DC 바이어스 전압이 인가되지 않을 때("w/o DC bias") 전극들 사이의 전위 프로파일을 보여주고, (b)는 상기 전극들 사이의 플라즈마 분포의 개략적인 도시이다. 도시의 용이함을 위해, 방위는 반시계방향으로 90도 회전되었음에 주목하라.
도 8은 본 발명의 구현예에 따른 개략적인 공정 순서를 보여주는 데, 여기서 단계 상승선은 온(ON) 상태 또는 양 증가 상태를 나타내고, 반면에 단계 하강선은 오프(OFF) 상태 또는 양 감소 상태를 나타내며, 각 부분의 높이 및 지속시간은 반드시 도시된 축척이지는 않다.
도 9는 본 발명의 구현예에 따라 부바이어스 전압의 양과 하부 유기막에 대한 손상 사이 및 부바이어스 전압의 양과 유기막 상에 증착된 SiCNO막의 습식 식각율 사이의 매우 간략화된 관계를 보여주는 그래프이다.
본 개시에서, "가스"는 증기화된 고체 및/또는 액체를 포함할 수 있으며, 맥락에 따라 단일 가스 또는 가스 혼합물로 구성될 수 있다. 유사하게, 단수형 명사는, 맥락에 따라 하나의 종(species) 또는 여러 종들을 포함하는 하나의 속(genus)을 지칭한다. 본 개시에서, 샤워헤드를 통해 공정 챔버로 유입되는 증착용 공정 가스는 실리콘-함유 전구체 및 첨가 가스로 구성되거나, 본질적으로 이루어지거나, 또는 이루어질 수 있다. 첨가 가스는, RF 전력이 첨가 가스에 인가될 때, 전구체를 산화, 질화 및/또는 탄화시키기 위한 반응물 가스 및 전구체를 여기시키기 위한 불활성 가스(예를 들면, 귀 가스)를 포함할 수 있다. 불활성 가스는 캐리어 가스 및/또는 희석 가스로서 반응 챔버에 공급될 수 있다. 또한, 일부 구현예에서, 반응물 가스는 사용되지 않고, 오직 귀(noble) 가스(캐리어 가스 및/또는 희석 가스로서)가 사용된다. 전구체 및 첨가 가스는 혼합 가스로서 또는 개별적으로 반응 공간에 유입될 수 있다. 전구체는 희유 가스(rare gas)와 같은 캐리어 가스와 함께 유입될 수 있다. 공정 가스 이외의 가스, 즉 샤워헤드를 통과하지 않고 유입되는 가스는, 예를 들면 반응 공간을 씰링하기 위해 사용될 수 있고, 희유 가스와 같은 씰 가스를 포함한다. 일부 구현예에서, 용어 "전구체"는 다른 화합물을 생성하는 화학 반응에 참여하는 화합물을 일반적으로 지칭하고, 특히 막 매트릭스 또는 막의 주골격을 구성하는 화합물을 지칭하며, 반면 용어 "반응물"은 전구체 이외의 화합물을 지칭하는데, 이 화합물은 전구체와 관련하여 사용되고, 전구체를 활성화시키거나, 전구체를 개질하거나, 전구체의 반응을 촉진시키며, 이러한 반응물은 RF 전력이 인가될 때 원소(예컨대, O)를 막 매트릭스에 제공할 수 있고, 막 매트릭스의 일부가 될 수 있다. 용어 "불활성 가스"는 RF 전력(또는 다른 전자기 에너지)이 인가되지 않을 때 불활성이지만 RF 전력(또는 다른 전자기 에너지)이 인가될 때 전구체를 여기시키거나 막을 개질하도록 플라즈마 상태가 될 수 있는 가스를 지칭하지만, 반응물과는 달리, 불활성 가스는 막 소지(matrix)의 일부가 되지 않을 수 있고 혹은 막 소지에 결합되지 않을 수 있다.
일부 구현예에서, "막"은 실질적으로 핀홀 없이 두께 방향에 수직한 방향으로 연속적으로 연장되어 전체 타켓 또는 관심 표면을 커버하는 층, 또는 단순히 타켓 또는 관심 표면을 커버하는 층을 지칭한다. 일부 구현예에서, "층"은 표면에 형성된 특정 두께를 갖는 구조물을 지칭하거나, 막 또는 막이 아닌 구조물의 동의어를 지칭한다. 막 또는 층은 특정 특성을 갖는 별개의 단일막 또는 층, 또는 다수의 막들 또는 층들로 구성될 수 있고, 인접하는 막들 또는 층들 사이의 경계는 명확하거나 그렇지 않을 수 있으며, 물리적, 화학적, 및/또는 임의의 특성, 형성 공정 및 시퀀스, 및/또는 인접하는 막들 또는 층들의 기능 또는 목적에 기반하여 구축될 수 있다. 또한, 본 개시에서, 실행 가능한 범위는 일상적인 작업에 기초하여 결정될 수 있으므로 변수의 임의의 두 수치가 변수들의 실행 가능한 범위를 구성할 수 있고, 지시된 임의의 범위는 끝점을 포함하거나 배제할 수 있다. 추가적으로, 지시된 변수의 임의의 값은 ("약"으로 표시되는지의 여부에 관계없이) 정확한 값 또는 대략적인 값을 지칭할 수 있고 등가를 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. 본 개시에서, 임의의 정의된 의미들은 일부 구현예에서 반드시 보통의 그리고 관습적인 의미들을 배제하는 것은 아니다.
조건 및/또는 구조가 명시되지 않는 본 개시에서, 당업자는 일상적인 실험에 따라 본 개시의 관점으로 이러한 조건 및/또는 구조를 쉽게 제공할 수 있다.
개시된 모든 구현예들에서, 하나의 구현예에 사용된 임의의 요소는 이와 동등한 임의의 요소로 대체될 수 있으며, 의도된 목적을 위해, 본원에 명시적으로, 필연적으로, 또는 내재적으로 개시된 것들을 포함한다. 또한, 본 발명은 장치 및 방법에 동일하게 적용될 수 있다.
구현예는 바람직한 구현예에 대해 설명될 것이다. 그러나, 본 발명은 그러한 바람직한 구현예에 한정되지 않는다.
위에서 논의된 바와 같이, 일부 구현예들에서, 서로 마주보는 용량 결합성 제1 및 제2 전극에 의해 정의된 반응 공간에서 플라즈마 강화 원자층 증착(PEALD)에 의해 기판 상에 막을 형성하는 방법에 있어서, 상기 기판은 상기 제2 전극과 마주보는 상기 제1 전극 위에 놓이고, 상기 PEALD는 증착 사이클들을 포함하며, 상기 증착 사이클들 각각은 다음 단계들을 포함한다: (i) 전구체를 상기 반응 공간에 펄스로 공급하여 상기 기판의 표면 상에 상기 전구체를 흡착시키는 단계; (ii)단계 (i) 후에, 상기 제2 전극에 RF 전력을 인가하여 상기 반응 공간에 상기 전구체가 흡착된 기판이 노출되는 플라즈마를 발생시켜서 상기 표면 상에 서브층을 형성하는 단계; 및 (iii) 단계 (ii)에서 RF 전력을 인가하는 동안 상기 제2 전극에 바이어스 전압을 인가하는 단계로서, 상기 바이어스 전압은 상기 제1 전극의 표면 위의 전위에 대하여 부(negative)이고, 상기 사이클은 다수의 서브층으로 구성되는 막이 원하는 두께를 가질 때까지 상기 다수의 서브층을 증착하기 위해 반복되는, 단계.
일부 구현예들에서, 상기 바이어스 전압은 DC 전압이다. 일부 구현예들에서, 상기 바이어스 전압은 1 MHz 이하의 주파수를 가지며 그의 평균 전압이 0이 아닌 AC 전압이다. 전형적으로, 상기 바이어스 전압은 DC 전압이지만, 이온들이 전류의 변화를 뒤따라가기만 하면, 상기 바이어스 전압은 AC 전압 또는 RF 전력, 예컨대 1 MHz 이하의 주파수를 갖는 AC 전압 또는 RF 전력일 수 있다.
일부 구현예들에서, 제1 전극은 접지되고, 이 때 바이어스 전압뿐만 아니라 RF 전력은 제2 전극에만 인가된다. 일부 구현예들에서, 상이한 주파수를 갖는 RF 전력은 제1 전극과 제2 전극에 각각 인가되고, 바이어스 전압은 제2 전극에만 인가된다.
일부 구현예들에서, 단계 (ii)에서, 플라즈마는 수소 플라즈마이다. 일부 구현예들에서, 단계 (ii)에서, 플라즈마는 H2, N2, O2, NH3, NxHy(x 및 y는 정수), N2O, NO2, CO2 및 귀 가스로 구성되는 군으로부터 선택되는 하나 이상의 가스 및 상기한 것들 중 하나의 혼합물의 플라즈마이다. 일부 구현예들에서, 단계 (ii)에서, 상기 플라즈마는 임의의 적합한 가스의 플라즈마인 데, 그 이유는 부바이어스 전압을 이용하는 플라즈마 전위의 감소, 즉 이온 에너지의 감소에 의한 효과가 가스의 종류에 상관 없이 이루어질 수 있기 때문이다.
일부 구현예들에서, 상기 바이어스 전압의 평균값은 0 V를 초과(예컨대, 10 V 이상)하지만 1,000 V 미만인 데, 이 때 상기 바이어스 전압은 상기 제1 전극의 표면 위의 전위에 대하여 부인 방식으로 인가된다(본 개시에서, 바이어스 전압은 절대값으로 표현되고, 용어 "부(negative)"는 달리 특정되지 않으면, 제1 전극과 제2 전극 사이의 전위를 감소시키는 인가 방향을 지칭한다). PEALD를 위한 공정 조건(예컨대, 50 내지 1,000 W의 RF 전력(13.56 MHz), 30 내지 3,000 Pa의 압력)은 변하기 때문에, 바이어스 전압의 평균값은 선택된 공정 조건(예컨대, HF 용액을 이용한 습식 식각율) 하에서 증착된 막의 품질 및/또는 하부층의 TEM 단면 영상에 의해 평가된 그 하부층(예컨대, 유기막)에 대한 손상도를 근거로 그에 따라 조절될 수 있다. 하부층(예컨대, 유기막)에 대한 손상도를 감소시키기 위해, 높은 바이어스 전압이 사용될 수 있고, 반면에 증착된 막의 품질을 향상시키기 위해, 낮은 바이어스 전압(예컨대, 높은 압력 조건, 예컨대 3,000 Pa의 압력 하에서 0 전압을 포함)이 사용될 수 있다. 도 9는 위의 관계를 개략적으로 나타낸 그래프로서, 본 발명의 구현예에 따라 부바이어스 전압의 양과 하부 유기막에 대한 손상 사이 및 부바이어스 전압의 양과 유기막 상에 증착된 SiCNO막의 습식 식각율 사이의 매우 간략화된 관계를 보여준다. 위에서 논의된 관계를 고려하여, 일부 구현예들에서, 평균 바이어스 전압은 10 내지 500 V, 전형적으로는 10 내지 300 V 범위이다. 본 개시에서, 막의 성질은, 거기에 제한되지는 않지만, 습식 식각에 대한 저항을 포함하는 데, 이러한 저항은 전형적으로 1/100 내지 1/200의 희석율을 가진 DHF(희석된 불화수소)의 용액에 막을 담구어서 평가할 수 있다(일부 구현예들에서, 10 내지 50℃(바람직하게는 15 내지 30℃)의 온도에서 1초 내지 5분(바람직하게는 1 내지 3분)의 식각 지속시간 동안, 0.1 내지 5 nm/분(바람직하게는 0.5 내지 2 nm/분)의 식각율로 HF 0.05~5%의 식각 용액을 사용).
일부 구현예들에서, 바이어스 전압의 사용은 표적이 되는 막, 예컨대 산화물막, 질화물막, 또는 탄소막이 이온 충돌에 민감할 때 그리고/또는 상기 표적이 되는 막이 직접 증착되는 하부막이 고분자막 또는 비정질 실리콘막일 때 특히 효과적이다.
일부 구현예들에서, 단계 (iii)에서, 상기 바이어스 전압은 사이클이 반복될 때 점차적으로 감소된다. 본 개시에서, 용어 "점차적으로 증가하는(또는 감소하는)"은, 구현예들에 따르면, 연속적으로 증가하는(또는 감소하는), 특정한(결정가능한) 율로 증가하는(또는 감소하는), 회귀 방정식이 데이터 값들을 이용하여 도출될 때 연속적으로 증가하는(또는 감소하는), 또는 데이터 값들이 마치 곡선 또는 대략 직선을 따라 플로트되는 것처럼 증가하는(또는 감소하는), 또는 증착된 막, 하부막, 증착 공정 등에 따라서 데이터를 보기좋게 할 때 연속적으로 증가하는(또는 감소하는) 것을 지칭한다. 도 6은 DC 바이어스 전압이 (a)에서 공정 사이클의 진행에 따라 변하고, 즉 (b)에서 이온 에너지가 공정 사이클의 진행에 따라 변하는 구현예를 도시한다. 도 6에 도시된 바와 같이, 상기 막을 특정 막, 예컨대 고분자막 위에 증착할 때, 하부층이 이온 충돌에 특히 취약한 시작 시에 증착 막이 여전히 얇기 때문에 고분자 식각을 억제하기 위해 (b)에 도시된 바와 같이 이온 에너지는 시작 시에 낮을 수 있다(즉, 바이어스 전압은 (a)에 도시된 바와 같이 시작 시에 높을 수 있다). 그 후, 공정 사이클이 반복됨에 따라 이온 충돌의 영향은 줄어들기 때문에, 증착 중인 막의 품질을 높이기 위해 상기 바이어스 전압은 감소될 수 있다. (a)에 도시된 바와 같이, 시작 시에 상기 바이어스 전압을 공급하고 이후 점차적으로 그 전압을 감소시킴으로써, 증착 중인 막의 품질을 높이면서 하부층에 대한 손상을 감소시키는 것이 가능하다.
일부 구현예들에서, 도 6에 도시된 바와 같이, 증착 사이클들은 제1 증착 사이클들((a)에서 단계 "a")로서 수행되고, PEALD는 제2 증착 사이클들((a)에서 단계 "c")을 더 포함하고, 상기 제2 증착 사이클들의 각 사이클은, (a)에서 상기 제1 증착 사이클들 후 중간 또는 천이 단계 "b"를 통하여 수행되는 단계 (iii) 없이(또는 실질적으로 단계 (iii) 없이, 즉 상기 바이어스 전압이 실질적으로 또는 거의 0임) 단계 (i)과 (ii)를 더 포함한다. 일부 구현예들에서, 상기 중간 증착 사이클들은, 상기 사이클이 반복될 때 상기 바이어스 전압이 점차적으로 감소하는(예컨대, 사이클 당 약 -1 내지 -20 V, 전형적으로는 사이클 당 약 -10 V) 단계 (i) 내지 (iii)을 포함하고, 상기 중간 증착 사이클들은 상기 제1 증착 사이클들 후에 연속적으로 수행되고, 상기 제2 증착 사이클들은 상기 중간 증착 사이클들 후에 연속적으로 수행된다. 본 개시에서, "연속적으로"는, 진공 파괴가 없으며, 시간대(timeline)로서의 중단이 없고, 임의의 물질의 개입 단계가 없으며, 다음 단계로서 그 직후에 처리 조건의 변경이 없고, 또는 구현예에 따라서는 두 개의 구조물 사이에 두 개의 구조물 이외의 분리된 물리적 또는 화학적 구조물이 개입하지 않음을 지칭한다. 일부 구현예들에서, 상기 제1 증착 사이클들은 막의 두께가 10 nm 이하(예컨대, 5 nm 이하, 3 nm 이하, 적어도 1 nm, 2 nm 이상)일 때 종료된다. 도 6에 도시된 순서가 탄소막 위의 SiO 막을 이용하는 이중 패터닝 공정에 적용되면, 단계 "a"는 약 30 사이클로 구성되고(약 2 nm의 두께를 갖는 보호막을 형성), 단계 "b"는 약 30 사이클로 구성되고(하부층, 탄소막이 손상되지 않는 정도까지 이온 에너지를 증가시킴으로써 약 2 nm의 두께를 갖는 SiO막을 형성), 및 단계 "c"는 약 240 사이클로 구성(막 증착을 위해 최적화된 조건 하에서 약 16 nm의 두께를 갖는 SiO막을 형성)된다.
일부 구현예들에서, 반응 가스 및 캐리어 가스/희석 가스는 단계 (i) 내지 (iii)동안 내내 반응 공간에 연속적으로 공급된다. 일부 구현예들에서, 상기 사이클은 단계 (i)이 지날 때마다 그리고 단계 (ii)가 지날 때마다 퍼징하는 단계를 더 포함한다. 도 8은 본 발명의 구현예에 따른 개략적인 공정 순서를 보여주는 데, 여기서 단계 상승선은 온(ON) 상태 또는 양 증가 상태를 나타내고, 반면에 단계 하강선은 오프(OFF) 상태 또는 양 감소 상태를 나타내며, 각 부분의 높이 및 지속시간은 반드시 도시된 축척이지는 않다. 이러한 공정 순서에서, 증착 공정은 Si 웨이퍼를 수용하고 있는 CCP-형 반응 챔버에서 수행된다. 단계 "피드(Feed)", "퍼지 1", "RF", 및 "퍼지 2"는 PEALD의 한 사이클을 구성한다. "피드", "퍼지 1", "RF", 및 "퍼지 2"를 통하여 반응 가스(예컨대, O2) 및 희석 가스/캐리어 가스(예컨대, Ar)를 연속적으로 공급하면서, "피드"에서, 웨이퍼의 표면에 전구체를 화학흡착시키기 위해 전구체(예컨대, 알킬아미노실란)를 반응 챔버에 펄스로 공급한다. "RF"에서, 전구체가 흡착된 웨이퍼를 상기 반응 가스의 플라즈마에 노출시킴으로써 상기 웨이퍼의 표면 상에 단층을 형성하기 위해 RF 전력이 인가된다. "퍼지 1" 및 "퍼지 2"는 반응하지 않은 성분들 및 부산물들을 기판으로부터 제거하기 위한 퍼징 단계들로서, 상기 반응 가스 및 희석 가스/캐리어 가스의 연속적인 유동은 퍼징 가스로서 기능한다. 본 구현예에서, "RF"에서 RF 전력이 인가되는 동안 완전하게 DC 바이어스 전압이 상부 전극에 인가된다. 즉, RF 전력의 "온(ON)" 시점과 DC 바이어스 전압의 "온" 시점은 완전하게 또는 실질적으로 일치하고, 그 결과 플라즈마의 이온 에너지는 "RF"의 전체 기간에 걸쳐서 제어될 수 있다. 본 개시에서, "실질적으로 동일한", "실질적으로 균일한" 등은 무형의 차이 또는 당업자에 의해 인식되는 차이, 예컨대 10% 미만, 5% 미만, 1% 미만, 또는 일부 구현예에 따라서는 이들의 임의의 범위를 지칭할 수 있다. 또한, 용어 "실질적으로 일치하는(substantially synchronized)"은 제어 회로에서 불가피한 응답 또는 시간 지연을 포함한다. 대안적으로, DC 바이어스 전압은 이온 에너지가 높지 않을 때 RF 전력의 펄스의 기간 동안 펄스들로 또는 짧은 펄스로 인가될 수 있다. 한 사이클은 웨이퍼 위에 원하는 두께의 막이 얻어질 때까지 반복된다.
일부 구현예들에서, PEALD 사이클은 아래의 표 1에 나타낸 조건하에서 수행된다.
(수치는 근사치임)
PEALD 사이클을 위한 조건
기판 온도 100 내지 500℃(바람직하게는 200 내지 400℃)
전극 갭(기판의 두께는 약 0.7 mm임) 3 내지 15 mm(바람직하게는 7 내지 12 mm)
압력 50 내지 3000 Pa(바람직하게는 200 내지 1000 Pa)
반응가스의 유량(연속적) 0.1 내지 4 sccm(바람직하게는 0.5 내지 1 sccm)
캐리어 가스의 유량(연속적) 1 내지 4 sccm(바람직하게는 1.5 내지 3 sccm)
희석 가스의 유량(연속적) 0.1 내지 3 slm(바람직하게는 0.5 내지 1.5 slm)
전구체의 유량 캐리어 가스의 유량에 대응함
300-mm 웨이퍼를 위한 RF 전력 13.56 내지 100 MHz(바람직하게는 13.56 MHz)50 내지 1000 W(바람직하게는 100 내지 400 W)
바이어스 전압 DC 10 내지 1000 V(바람직하게는 10 내지 200 V); AC(1 MHz 이하의 주파수) 평균 10 내지 1000 V(바람직하게는 10 내지 200 V)
"피드"의 지속시간 0.1 내지 1초 (바람직하게는 0.1 내지 0.5초)
"퍼지 1"의 지속시간 0.5 내지 2초 (바람직하게는 0.5 내지 1초)
"RF"의 지속시간 0.5 내지 10초 (바람직하게는 1 내지 5초)
"퍼지 2"의 지속시간 0.1 내지 2초 (바람직하게는 0.1 내지 1초)
한 사이클의 지속시간 1.1 내지 15초 (바람직하게는 1.7 내지 7.5초)
사이클당 글로우(glow) 속도(nm/min) 최상부면 상에서 0.01 내지 0.1
상기 제1 전극의 표면 위 전위에 대하여 부전압으로서 RF 전력을 인가하는 동안, 바이어스 전압이 상기 제2 전극에 인가된다.
위에서 표시된 300-mm 웨이퍼용 RF 전력은 W/cm2(웨이퍼의 단위 면적당 전력량)으로 변환될 수 있고, 이는 200 mm 또는 450 mm와 같은 다른 직경을 갖는 웨이퍼에 적용할 수 있다.
전형적으로, 유전체 막의 두께는 약 50 nm 내지 약 500 nm의 범위이다(원하는 막 두께는 막의 응용 및 목적 등에 따라 적절하다고 여겨지는 것으로 선택될 수 있음). 상기 유전체 막은 이중 패터닝을 위해 사용될 수 있다.
상기한 공정은 스페이서 정의 이중 패터닝(SDDP)을 비롯하여 다양한 공정에서 사용될 수 있는 데, 개시된 구현예들 중 하나에 따른 실리콘 산화물막 또는 그의 등가물들은 수직 스페이서로서 사용될 수 있다.
일부 구현예들에서, 상기 기판은 리세스 패턴을 가지는 데, "트렌치"로서 지칭되는 각 리세스는 인접한 수직 스페이서들 사이에 정의되고 바닥과 측벽들에 의해 구성된다. 즉, 트렌치는 수직 스페이서로 형성된 패턴을 포함하는 임의의 리세스 패턴이고, 일부 구현예에서, 약 10 nm 내지 약 100 nm의 폭(전형적으로 약 14 nm 내지 약 30 nm)(여기서, 트렌치의 길이가 실질적으로 폭과 동일할 때, 이는 홀/비아(via)로 지칭되며, 이들의 직경은 약 10 nm 내지 약 100 nm임), 약 30 nm 내지 약 100 nm의 깊이(전형적으로 약 40 nm 내지 약 60 nm), 그리고 약 2 내지 약 20의 종횡비(전형적으로 약 2 내지 약 5)를 갖는다. 트렌치의 적절한 치수는 공정 조건, 막 조성물, 의도된 용도 등에 따라 달라질 수 있다.
일부 구현예들에서, 상기 리세스 패턴 내에 증착된 막은 80% 내지 100%, 전형적으로는 90% 이상의 등각성(최상부면 또는 바닥면 상에 증착된 막의 두께에 대한 측벽들 상에 증착된 막의 두께의 비)을 가진다.
공정 사이클은, 예를 들어 도 1에 예시된 장치를 포함하는 임의의 적절한 장치를 사용하여 수행될 수 있다. 도 1은 본 발명의 구현예에 따라, 바람직하게는 아래에 기술된 순서들을 수행하도록 프로그램된 제어 동작들과 관련하여, 부바이어스 전압을 갖는 단일 주파수 RF 전력을 사용하여 유전체 막을 증착하기 위한 PEALD(plasma-enhanced atomic layer deposition)의 개략적인 묘사이다.
이 도면에서, 서로 마주하며 평행한 한 쌍의 전기 전도성 평판 전극(4, 2)을 반응 챔버(3)의 내부(반응 구역)(11)에 제공하고, HRF 전력(예컨대, 13.56 MHz, 27 MHz, 60 MHz, 100 MHz, 및 상기한 임의의 두 수치들 사이의 임의 값들을 비롯하여 2 내지 100 MHz)(20)을 일측에 인가하고 타측(12)을 전기적으로 접지시킴으로써, 플라즈마가 전극들 사이에서 여기된다. 온도 조절기가 하부 스테이지 또는 서셉터(2)(하부 전극)에 제공되고, 그 위에 놓인 기판(1)의 온도는 주어진 온도로 일정하게 유지된다. 상부 전극(4)은 샤워 플레이트(shower plate)로서의 역할도 수행하며, 반응물 가스 및/또는 희석 가스, 그리고, 만약에 존재한다면, 전구체 가스가 각각의 가스 라인(21) 및 가스 라인(22)을 통해서 그리고 샤워 플레이트(4)를 통해서 반응 챔버(3)로 유입된다. 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, 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 씰 가스를 유입하기 위한 씰 가스 라인(24)을 구비하며, 반응 구역과 이송 구역을 분리하기 위한 분리 판(14)이 제공된다(웨이퍼가 이송 챔버(5)로 또는 이송 챔버(5)로부터 이송되는 게이트 밸브는 본 도면에서 생략됨). 이송 챔버는 또한 배기 라인(6)을 구비한다. 일부 구현예에서, 다중-요소 막의 증착 및 증착 후처리는 동일한 반응 공간에서 수행되므로, 모든 단계들이 기판을 공기 또는 다른 산소-함유 대기에 노출시키지 않고 연속적으로 수행될 수 있다.
이러한 장치에서, 부의 바이어스 전압이 블로킹 커패시터(RF 컷(cut) 필터 또는 로우 패스 필터)(32)를 통하여 DC 전력 공급부(31)로부터 샤워 플레이트(4)에 인가된다. RF 전력을 인가하는 시점과 바이어스 전압을 인가하는 시점은 RF 전력원(20), 전력원(20), 블로킹 커패시터(32), 및 DC 전력 공급부(31)의 출력측에 배치된 매칭 박스(30)를 제어하는 제어 유닛(34)을 사용하여 실질적으로 일치된다. 제어 유닛(34)은 전극들 사이의 전위를 측정하는 전극 전위 측정 유닛(33)으로부터 신호를 수신하여 전극 전위에 따라 상기한 구성 요소들을 제어할 수 있다. 상부 전극에 인가될 바이어스 전압의 값은 DC 전압계를 사용하여 측정될 수 있다. 도 3은 본 발명의 구현예에 따라 바이어스 전압을 결정하기 위한 전위의 직류 성분을 측정하기 위한 전류의 개략적인 묘사이다. DC 전압계(27)는 초크 코일(28)(로우 패스 필터(32)) 뒤에 놓이므로, 전위의 DC 성분이 추출되어 DC 전압계(27)를 통과할 수 있다.
상기한 구성은 이중 주파수 RF 전력 시스템에 적용될 수 있다. 도 2는 본 발명의 구현예에 따라 부바이어스 전압을 갖는 이중 주파수 RF 전력을 사용하여 유전체 막을 증착하기 위한 PEALD(plasma-enhanced atomic layer deposition)의 개략적인 묘사이다. 이러한 장치에서, 제2 RF 전력원(36)은 매칭 박스(37)를 통하여 하부 전극(2)에 연결되고, 제어 유닛(35)은 위에서 기술된 구성 요소들 외에도 매칭 박스(37)와 제2 RF 전력원(36)을 제어한다.
도 7(반시계방향으로 90° 회전된 방위)은 구현예를 도시하는 데, (a)는 부의 DC 바이어스 전압이 상부 전극에 인가될 때("w/DC bias")와 부의 DC 바이어스 전압이 인가되지 않을 때("w/o DC bias") 전극들 사이의 전위 프로파일을 보여주고, (b)는 상기 전극들 사이의 플라즈마 분포의 개략적인 도시이다. 일반적으로, 플라즈마의 전자 온도는 이온들의 온도보다 높기 때문에, 가볍고 빨리 이동하는 전자들로 인하여 벽면 전위는 플라즈마 전위에 대하여 보통 부(negative)이다. 즉, 플라즈마 전위는 벽면 전위에 대하여 보통 정(positive)이다. 본 개시에서, 전압의 값은 하부 전극(2)의 벽면 전위를 기준으로 결정된다. 즉, 하부 전극(2)의 벽면 전위는 0으로 간주된다. 벽면 상에, 이온 쉬스(sheath)가 발생되는 데, 상기 쉬스는 과량의 이온들이 존재하는 곳에서 전자들의 속도를 낮추거나 전자들을 반사하고 이온들의 속도를 높여서 플라즈마가 전체적으로 전기적 중성으로 유지되는 공간 전하층이다. 도 7의 (a)에 도시된 바와 같이, RF 전력이 상부 전극(4)에 인가되는 동안 DC 바이어스 전압이 상부 전극(4)에 인가되지 않을 때("w/o DC 바이어스"), 상부 전극(4)의 벽면 전위는 하부 전극(2)의 벽면 전위(0)에 대하여 부인 V0dc이고, 플라즈마 전위는 상부 전극과 하부 전극의 벽에 인접한 영역들을 제외하면 정(positive)이다(플라즈마 전위는 최대선 및 최소선을 이용하여 표현된다). RF 전력이 상부 전극(4)에 인가되는 동안 DC 바이어스 전압이 상부 전극(4)에 인가되지 않을 때("w/o DC 바이어스"), 상부 전극(4)의 벽면 전위는 하부 전극(2)의 벽면 전위(0)에 대하여 부인 V0dc이고, 플라즈마 전위는 상부 전극과 하부 전극의 벽에 인접한 영역들을 제외하면 정(positive)이다(플라즈마 전위는 최대선 및 최소선을 이용하여 표현되지만, 나머지 영역에서는 하나의 선으로 표시되는 데, 그 이유는 최대 및 최소 사이의 차이가 작고, 하나의 선으로 간략화 되어 근사치로 될 수 있기 때문이다). Vdc는 바이어스 전압 값인 Vdc(=V1dc)와 V0dc의 합이다. 도 7의 (a)에 도시된 바와 같이 바이어스 전압을 인가함으로써, 상부 이온 쉬스의 두께는 더 두껍게 되고, 반면에 하부 이온 쉬스의 두께는 더 얇게 된다. 그 결과, 도 7의 (b)에 도시된 바와 같이, 반응 챔버(3)의 내부(11)에 형성된 상부 이온 쉬스(53)에서, 벽면은 이차 전자들(51)의 증가를 유도하는 이온들(45)에 의한 강한 이온 충돌(높은 이온 에너지)에 노출된다. 반면에, 하부 전극(2) 근처의 플라즈마(52)의 타측 위에 형성된 하부 이온 쉬스(54)에서, 하부 이온 쉬스(54)의 두께는 얇아지고, 벽면 위의 기판(1)은 이온들에 의한 이온 충돌에 덜 노출된다.
바이어스 전압의 인가 결과, 하부 이온 쉬스(54)는 낮은 이온 에너지(더 낮은 이온 충돌)를 가지기 때문에, 하부층의 손상 또는 식각은 효과적으로 억제되거나 감소될 수 있다. 반면에, 상부 이온 쉬스(53)는 강한 이온 충돌로 인하여 방출된 이차 전자들에 의해 유도되는 높은 플라즈마 밀도를 가지기 때문에, 높은 플라즈마 밀도의 상태는 플라즈마(52)를 통하여 유지될 수 있고, 하부 이온 쉬스(54)에서 플라즈마 밀도를 증가시킬 수 있어서, 결국 처리량이 더 많아진다. 하부 이온 쉬스(54)에서, 기판 표면은 이온 충돌에 덜 노출되지만, 이온 밀도는 높은 플라즈마 밀도(높은 이온량)로 인해 높아서, RF 전력의 지속시간은 짧아질 수 있고, 그 결과 처리량이 더 많아진다. 또한, 상부 전극(4)의 표면은 강한 이온 충돌에 노출되기 때문에, 상기 표면 상에서의 막 성장은 억제되고, 그 결과 입자 발생이 줄어들게 된다. 아울러, 상부 이온 쉬스(53)에서 방출된 이차 전자들은 증가되고 거기로부터 발생된 플라즈마 종은 상부 이온 쉬스(53) 전체에 걸쳐서 분산되기 때문에, 플라즈마 균일도는 상당히 개선될 수 있다.
일부 구현예들에서, 상부 전극의 표면은 강한 이온 충돌에 노출되기 때문에, 강한 이온 충돌로 인해 스퍼터링에 의해 상기 표면으로부터 금속 오염물들이 발생될 수 있고, 결과적으로 기판 위에 형성된 막의 금속 오염물이 증가하게 된다. 이러한 경향은 바이어스 전압이 증가함에 따라 더욱 분명해진다. 따라서, 일부 구현예들에서, 상부 전극의 표면은 상기 기판 상에 형성될 막과 동일한 막인 사전 코팅으로서의 막으로 미리 덮여진다.
아래의 작용 실시예를 참조하여 본 발명을 더 설명한다. 그러나, 이러한 실시예는 본 발명을 제한하려는 의도는 아니다. 조건 및/또는 구조가 명시되지 않는 본 실시예에서, 당업자는 일상적인 실험에 따라 본 개시의 관점으로 이러한 조건 및/또는 구조를 쉽게 제공할 수 있다. 또한, 특정한 실시예에 적용된 수치들은 일부 구현예에서 적어도 ±50%의 범위로 수정될 수 있으며, 이러한 수치들은 근사치이다.
실시예
실시예 1(예언적)
유기막(폴리이미드 막)을 갖는 Si 기판(300 mm의 직경과 0.7 mm의 두께를 가짐) 위에, 약 30 nm의 두께를 갖는 SiOCN 막이 도 1, 3, 및 4에 도시된 장치를 사용하는 PEALD에 의해 도 8에 도시된 순서를 사용하여, 아미노실란((3-아미노프로필)트리메톡시실란, APTMS)을 전구체로서, H2를 반응물(H2 플라즈마)로서, 그리고 Ar을 캐리어 가스로서 사용하는 조건 하에서 증착되고, 상기 전구체를 위한 용기의 온도는 상온으로 설정되고, H2의 유량은 약 100 sccm이고, Ar 가스의 유량은 약 600 sccm이고, 압력은 약 4 Torr이고, 기판 온도는 약 200℃이다. 상부 전극에 인가된 RF 전력(13.56 MHz의 주파수)은 약 200 W이다.
실시예들에서 RF 전력과 중첩되도록 바이어스 전압이 0 V, -50 V, -100 V, -200 V, 및 -300 V의 전압을 이용하여 상부 전극에 각각 인가된다. 막 증착이 완료된 후, 바이어스 전압에 의한 전체적인 개선을 판단하기 위해 결과적인 SiOCN 막의 품질과 하부 폴리이미드막에 대한 손상 정도가 평가된다. SiOCN 막의 품질은 DHF를 이용한 습식 식각율에 의해 평가되고, 폴리이미드 막에 대한 손상 정도는 막의 TEM(투과 전자 현미경) 단면 이미지를 기반으로 평가된다. 각 평가점을 플로팅함으로써, 도 9 등에 도시된 관계가 얻어질 수 있고, 따라서 최적의 조건들이 결정될 수 있다.
실시예 2(예언적)
바이어스 전압이 도 6에 도시된 것처럼 변하는 것을 제외하면, 실시예 1과 유사한 방식으로 APTMS 를 전구체로서, H2를 반응물(H2 플라즈마)로서, Ar을 캐리어 가스로서 사용하여 300-mm Si 웨이퍼 위에 형성된 폴리이미드 막 위에 약 30 nm의 두께를 갖는 SiOCN이 증착된다. 즉, 단계 "a"에서는, 유기막에 대한 손상 정도가 최소인 실시예 1에서 결정된 바이어스 전압을 이용하여 SiOCN 막의 두께가 약 3 nm에 도달할 때까지 증착 사이클이 반복되고, 단계 "b"에서는, SiOCN 막의 품질이 최대(최적)인 실시예 1에서 결정된 바이어스 전압까지 부방향(예컨대, 약 -10 V/사이클)으로 점차적으로 증가되는 바이어스 전압을 이용하여 SiOCN 막의 두께가 약 5 nm(약 2 nm 추가)에 도달할 ?까지 증착 사이클은 계속해서 반복되고, 그 후 단계 "c"에서는, SiOCN 막이 최대(최적)인 실시예 1에서 결정된 바이어스 전압(0 포함)을 이용하여 SiOCN 막의 두께가 원하는 값에 도달할 때까지 증착 사이클은 연속적으로 반복된다. 그 결과, 하부 유기막에 대한 손상을 최소화하면서 고품질의 SiOCN 막이 성공적으로 증착된다.
당업자는 본 발명의 사상을 벗어나지 않고서 다수의 그리고 다양한 변형들이 만들어질 수 있음을 이해할 것이다. 따라서, 본 발명의 형태들은 단지 예시적인 것이며 본 발명의 범위를 한정하도록 의도된 것이 아니라는 것을 분명히 이해해야 한다.

Claims (15)

  1. 서로 마주보는 용량 결합성 제1 및 제2 전극에 의해 정의된 반응 공간에서 플라즈마 강화 원자층 증착(PEALD)에 의해 기판 상에 막을 형성하는 방법으로서, 상기 기판은 상기 제2 전극과 마주보는 상기 제1 전극 위에 놓이고, 상기 PEALD는 증착 사이클들을 포함하며, 상기 증착 사이클들 각각은 다음 단계들을 포함하고:
    (i) 전구체를 상기 반응 공간에 펄스로 공급하여 상기 전구체를 상기 기판의 표면 상에 흡착시키는 단계;
    (ii) 단계 (i) 후에, RF 전력을 상기 제2 전극에 인가하여 상기 반응 공간에 상기 전구체가 흡착된 표면이 노출되는 플라즈마를 발생시켜서 상기 표면 위에 서브층을 형성하는 단계; 및
    (iii) 단계 (ii)에서 RF 전력을 인가하는 동안, 상기 제1 전극의 표면 위 전위에 대하여 부(negative)인 바이어스 전압을 인가하는 단계,
    상기 서브층들로 구성되는 막이 원하는 두께를 가질 때까지 상기 사이클이 반복되어 다수의 서브층을 증착하는, 방법.
  2. 제1항에 있어서, 상기 바이어스 전압은 DC 전압인, 방법.
  3. 제1항에 있어서, 상기 바이어스 전압은 1 MHz 이하의 주파수를 가지며 그의 평균 전압이 0이 아닌 AC 전압인, 방법.
  4. 제1항에 있어서, 상기 제1 전극은 접지되는, 방법.
  5. 제1항에 있어서, 단계 (ii)는 RF 전력을 상기 제1 전극에 인가하는 단계를 더 포함하는, 방법.
  6. 제1항에 있어서, 단계 (ii)에서, 상기 플라즈마는 수소 플라즈마인, 방법.
  7. 제1항에 있어서, 상기 바이어스 전압의 평균값은 10 내지 1,000 V인, 방법.
  8. 제1항에 있어서, 상기 막은 산화물막, 질화물막, 또는 탄소막인, 방법.
  9. 제1항에 있어서, 단계 (i)을 거친 상기 기판은 상기 막이 직접 증착되는 하부막으로서 고분자막 또는 비정질 실리콘막을 갖는, 방법.
  10. 제1항에 있어서, 단계 (iii)에서, 상기 사이클이 반복될 때 상기 바이어스 전압은 점차적으로 감소되는, 방법.
  11. 제9항에 있어서, 상기 증착 사이클들은 제1 증착 사이클들이고, 상기 PEALD는 제2 증착 사이클들을 더 포함하고, 상기 제2 증착 사이클들 각각은 상기 제1 증착 사이클들 후에 수행되는 단계 (iii) 없이 단계 (i)과 (ii)를 포함하는, 방법.
  12. 제11항에 있어서, 상기 PEALD는, 단계 (i) 내지 (iii)를 비롯하여 상기 사이클이 반복될 때 상기 바이어스 전압이 점차적으로 감소하는 중간 증착 사이클들을 더 포함하고, 상기 중간 증착 사이클들은 상기 제1 증착 사이클들 후에 연속적으로 수행되고, 상기 제2 증착 사이클들은 상기 중간 증착 사이클들 후에 연속적으로 수행되는, 방법.
  13. 제9항에 있어서, 상기 제1 증착 사이클들은 상기 막의 두께가 10 nm 이하에 도달하면 종료되는, 방법.
  14. 제1항에 있어서, 반응 가스 및 캐리어 가스/희석 가스는 단계 (i) 내지 (iii) 동안 내내 상기 반응 공간에 연속적으로 공급되는, 방법.
  15. 제1항에 있어서, 상기 사이클은 단계 (i)가 지날 때마다 그리고 단계 (ii)가 지날 때마다 퍼징하는 단계를 더 포함하는, 방법.
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