KR20210024420A - 비스(디에틸아미노)실란을 사용하여 peald에 의해 개선된 품질을 갖는 실리콘 산화물 막을 증착하기 위한 방법 - Google Patents
비스(디에틸아미노)실란을 사용하여 peald에 의해 개선된 품질을 갖는 실리콘 산화물 막을 증착하기 위한 방법 Download PDFInfo
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Abstract
플라즈마 강화 원자층 증착(PEALD)에 의해 반응 공간 내의 기판 상에 비스(디에틸아미노)실란(BDEAS)을 사용하여 실리콘 산화물 막을 증착하는 방법에서, PEALD의 반복적인 증착 사이클 각각은, (i) 반응 공간 내의 BDEAS의 열분해를 실질적으로 억압하는 분위기에서 400°C 초과의 온도를 갖는 서셉터 상에 배치된 기판 상에 BDEAS를 흡착시키는 단계, 및 (ii) BDEAS가 위에 흡착된 기판을 반응 공간 내 분위기에서 산소 플라즈마에 노출시킴으로써 실리콘 산화물 단층 또는 하위층을 증착하는 단계를 포함한다.
Description
본 발명은 일반적으로 비스(디에틸아미노)실란(BDEAS)을 사용하여 플라즈마 강화 원자층 증착(PEALD)에 의해 개선된 품질(예, 특히 트렌치의 측벽 및 바닥에서 우수한 내화학성, 예컨대 낮은 습식 식각 속도)을 갖는 실리콘 산화물 막을 증착하는 방법에 관한 것이다.
PEALD에 의해 실리콘 산화물 막을 증착하는 방법으로서, BDEAS 및 산소 플라즈마를 사용한 증착 방법이 공지되어 있다. 그러나, 종래의 방법을 사용하여 기판 내에 형성된 트렌치에 실리콘 산화물 막을 증착하는 경우, 트렌치의 측벽 및 하부에서의 막 품질(내화학성, 예컨대 낮은 건식 또는 습식 식각 속도, 누설 전류, 수축, 평면 내 균일성 등)은 기판 상부 표면 상의 막 품질에 비해 불충분하거나 만족스럽지 않은 경향이 있다. 일반적으로, RF 전력 펄스의 지속 시간 및/또는 RF 전력을 증가시킴으로써, 막 품질이 개선될 것으로 예상된다. 그러나, 트렌치가 고 종횡비(예, 3 이상, 특히 10 이상)를 갖는 경우, 특히 트렌치의 측벽 및 하부에서의 막 품질에서, (예를 들어, 이온으로 구성된 직접식 플라즈마에 의한 이온 충돌에 의해) 플라즈마의 방향성 또는 이방성 성질로 인해 충분한 막 품질의 개선이 달성되지 않았다.
종래의 기술을 고려하여, 본 발명의 일 구현예는 BDEAS를 사용하여 PEALD에 의해 개선된 품질을 갖는 실리콘 산화물 막을 증착하기 위한 방법을 제공한다.
종래 기술과 연관된 문제 및 해결책에 대한 임의의 논의는 단지 본 발명에 대한 맥락을 제공하기 위해서만 본 개시에 포함되었고, 그 논의 중 어느 하나 또는 전부가 본 발명이 이루어진 당시에 공지된 것임을 인정하는 것으로 받아들여져서는 안된다.
전술한 바와 같이, 공정 파라미터로서, RF 전력 펄스의 지속 시간 및/또는 RF 전력을 증가시키는 것은, BDEAS를 사용하여 PEALD에 의해 실리콘 산화물 막을 증착하는 데 있어서, 트렌치의 측벽 및 하부에서의 막 품질을 개선시키는 데 충분하지 않거나 효과적이지 않을 수 있고, 이는 플라즈마의 이방성 성질에 기인하기 때문이다. 따라서, 공정 파라미터로서, 증착 온도를 증가시키는 것은 차선책으로 간주될 수 있다. 그러나, 당업자는, BDEAS가 400°C보다 높은 온도에서 열분해를 시작하고, 따라서 BDEAS를 사용해 고품질의 실리콘 산화물 막을 얻기 위해서 PEALD에서의 공정 온도는 바람직하게는 400°C 이하여야 하는 것으로 간주하는 경향이 있다. 예를 들어, 미국 특허 제8,227,032호는, 매우 낮은 탄소 및 수소 함량을 갖는 고품질 막이 200 내지 400℃에서 바람직하게 증착되는 것을 진술하고 있다. BDEAS가 열분해되면, 아민, 탄소의 산화물, 질소의 산화물, 및 실리콘의 산화물이 열분해 생성물로서 생성되어 탄소, 질소 및 수소의 비교적 높은 함량을 갖는 실리콘 산화물 막의 증착을 초래한다. 또한, 예를 들어 WO2016/954531은, 웨이퍼 표면이 약 450°C 내지 약 650°C 범위의 온도로 가열되어, 흡수된 실리콘 전구체는 웨이퍼 표면 상에서 열분해되어 단층 또는 단층에 준하는 실리콘 막을 형성함을 진술하고 있다. 전술한 바와 같이, 당업자는, BDEAS가 400°C 보다 높은 온도에서 열분해된다고 상당히 예상한다. 따라서, 탄소/질소를 함유한 흡착 실리콘 전구체가 산소 플라즈마와 반응하고 탄소/질소를 산소로 교체하는 교체 반응에 의해 실리콘 산화물 막을 형성하는 전형적인 PEALD와 달리, WO2016/954531에서, 먼저 흡착된 실리콘 전구체가 웨이퍼 표면 상에서 열분해되어 단층 또는 단층에 준하는 실리콘 막을 형성한 다음, 산소 공급원에 노출됨으로써, 실리콘 막을 산화시켜 SiO2 막을 형성하는 것에 유의해야 한다.
당업자의 예상과 다르게, 본 발명자는 BDEAS가 안정적이고 400°C 초과 650°C 미만의 온도에서 상당히 분해되지 않으며, PEALD에 의한 증착 온도로서 이러한 고온을 사용함으로써, 증착된 실리콘 산화물 막의 막 품질이 특히 트렌치의 측벽 및 하부에서 상당히 개선될 수 있음을 발견하였다. 일부 구현예에서, PEALD에 의해 반응 공간 내의 기판 상에 BDEAS를 사용하여 실리콘 산화물 막을 증착하는 방법에서, PEALD의 반복적인 증착 사이클 각각은, (i) 반응 공간 내 BDEAS의 열분해를 실질적으로 억압하는 분위기에서 400°C 초과의 온도를 갖는 서셉터 상에 배치된 기판 상에 BDEAS를 흡착시키는 단계, 및 (ii) BDEAS가 위에 흡착된 기판을 반응 공간 내 분위기에서 산소 플라즈마에 노출시킴으로써 실리콘 산화물 단층을 증착하는 단계를 포함한다.
일부 구현예에서, 서셉터의 온도는 650°C보다 낮다. 일부 구현예에서, 분위기는 1,000 Pa 이하의 압력 및 5% 내지 70%의 산소 농도를 갖는다. 또한, 일부 구현예에서, 분위기는 400 Pa 이하의 압력을 갖는다. 또한, 일부 구현예에서, 분위기는 30% 내지 60%의 산소 농도를 갖는다.
관련 기술을 넘어 달성된 본 발명의 양태 및 이점을 요약하기 위한 목적으로, 본 발명의 특정 목적 및 이점이 본 개시에서 설명된다. 물론, 이러한 모든 목적 및 이점이 본 발명의 임의의 특정 구현예에 따라 반드시 달성되는 것이 아니라는 것을 이해하여야 한다. 따라서, 예들 들면 당업자는 본 발명이 본원에 교시 또는 제시될 수 있는 다른 목적 또는 이점을 반드시 달성하지 않고, 본원에 교시된 바와 같은 하나의 이점 또는 여러 이점들을 달성하거나 최적화하는 방식으로 구현되거나 수행될 수 있다는 것을 인식할 것이다.
본 발명의 추가 양태, 특징, 및 이점은 다음의 상세한 설명으로부터 명백해질 것이다.
본 발명의 이들 특징 및 다른 특징은 이제 바람직한 구현예의 도면을 참조하여 설명될 것이고, 이는 예시를 위한 것이며 본 발명을 제한하기 위한 것은 아니다. 도면은 예시의 목적으로 매우 간략화되어 있으며, 축척에 반드시 비례하지는 않는다.
특허 또는 출원 파일은 컬러로 출력된 적어도 하나의 도면을 포함한다. 컬러 도면(들)을 갖는 본 특허 또는 특허 출원 공개의 사본은, 요청 및 필요한 수수료 결제시, 사무국에 의해 제공될 것이다.
도 1a는 본 발명의 구현예에 사용할 수 있는 실리콘 산화물 막을 증착하기 위한 PEALD(플라즈마 강화 원자층 증착)의 개략적인 표현이다.
도 1b는 본 발명의 구현예에 사용할 수 있는 유동 통과 시스템(FPS)을 이용한 전구체 공급 시스템의 개략적인 표현을 나타낸다.
도 2는, 본 발명의 구현예에 따른 하나에서 PEALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하는 반면에 흰색의 셀은 오프 상태를 표시하고, 각 열의 폭이 각 공정의 지속 시간을 표시하는 것은 아니다.
도 3은, 참조예 1에서 막 두께와 서셉터 온도 사이의 개략적인 관계를 표시하는 그래프를 나타낸다.
도 4는 상이한 온도에서 실리콘 산화물 막의 증착("증착 상태") 다음에 습식 식각("DHF 침지후")을 거친 트렌치 단면의 STEM 사진을 보여주는 차트이다.
도 5는 상이한 압력, 상이한 산소 농도, 및 상이한 퍼지 지속 시간에서 실리콘 산화물 막의 증착("증착 상태") 다음에 습식 식각("DHF 침지후")을 거친 트렌치 단면의 STEM 사진을 보여주는 차트이다.
도 6은, 도 4에 나타낸 증착에서 사용된 증착 조건과 최종 생성된 실리콘 산화물 막의 막 특성을 나타낸 차트이고, 막의 2D 컬러 맵 분석에 의해 박막 두께 프로파일 측정 이미지의 컬러 버전을 포함한다.
도 7은 본 발명의 구현예에 따라, 표면 상의 플라즈마 충돌과 습식 식각 속도의 관계를 보여주는 개략적인 그래프이다.
특허 또는 출원 파일은 컬러로 출력된 적어도 하나의 도면을 포함한다. 컬러 도면(들)을 갖는 본 특허 또는 특허 출원 공개의 사본은, 요청 및 필요한 수수료 결제시, 사무국에 의해 제공될 것이다.
도 1a는 본 발명의 구현예에 사용할 수 있는 실리콘 산화물 막을 증착하기 위한 PEALD(플라즈마 강화 원자층 증착)의 개략적인 표현이다.
도 1b는 본 발명의 구현예에 사용할 수 있는 유동 통과 시스템(FPS)을 이용한 전구체 공급 시스템의 개략적인 표현을 나타낸다.
도 2는, 본 발명의 구현예에 따른 하나에서 PEALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하는 반면에 흰색의 셀은 오프 상태를 표시하고, 각 열의 폭이 각 공정의 지속 시간을 표시하는 것은 아니다.
도 3은, 참조예 1에서 막 두께와 서셉터 온도 사이의 개략적인 관계를 표시하는 그래프를 나타낸다.
도 4는 상이한 온도에서 실리콘 산화물 막의 증착("증착 상태") 다음에 습식 식각("DHF 침지후")을 거친 트렌치 단면의 STEM 사진을 보여주는 차트이다.
도 5는 상이한 압력, 상이한 산소 농도, 및 상이한 퍼지 지속 시간에서 실리콘 산화물 막의 증착("증착 상태") 다음에 습식 식각("DHF 침지후")을 거친 트렌치 단면의 STEM 사진을 보여주는 차트이다.
도 6은, 도 4에 나타낸 증착에서 사용된 증착 조건과 최종 생성된 실리콘 산화물 막의 막 특성을 나타낸 차트이고, 막의 2D 컬러 맵 분석에 의해 박막 두께 프로파일 측정 이미지의 컬러 버전을 포함한다.
도 7은 본 발명의 구현예에 따라, 표면 상의 플라즈마 충돌과 습식 식각 속도의 관계를 보여주는 개략적인 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 또는 여러 종을 포함하는 하나의 속을 지칭한다. 본 개시에서, 샤워헤드를 통해 반응 챔버로 유입되는 공정 가스는 아미노실란 전구체 및 첨가 가스로 구성되거나, 본질적으로 이루어지거나, 또는 이루어질 수 있다. 전구체는 비스(디에틸아미노)실란(BDEAS)만 포함할 수 있거나, BDEAS를 일차 전구체로 그리고 실리콘 산화물을 형성하기 위해 BDEAS의 플라즈마 산화를 방해하지 않는 정도로만 아미노실란 또는 비아미노실란인 하나 이상의 이차 전구체(들)를 포함할 수 있다. RF 전력을 첨가 가스에 인가하는 경우, 첨가 가스는, 실리콘 산화물을 증착하도록 전구체를 여기시키기 위한 플라즈마 발생 가스를 포함할 수 있다. 첨가 가스는 전구체를 산화시키기 위한 반응물 가스를 함유할 수 있고, 캐리어 가스 및/또는 희석 가스로서 반응 챔버에 공급될 수 있는 불활성 가스를, 실리콘 산화물을 형성하는 플라즈마 산화를 방해하지 않는 정도로만 추가로 포함할 수 있다. 전구체 및 첨가 가스는 혼합 가스로서 또는 개별적으로 반응 공간에 유입될 수 있다. 전구체는 희귀 가스와 같은 캐리어 가스와 함께 유입될 수 있다. 공정 가스 이외의 가스, 즉 샤워헤드를 통과하지 않고 유입되는 가스는, 예를 들면 반응 공간을 밀폐하기 위해 사용될 수 있고, 희귀 가스와 같은 밀폐 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, 이는 전구체를 활성화시키거나, 전구체를 개질하거나, 전구체의 반응을 촉진시키며, 이러한 반응물은 RF 전력이 인가되는 경우에 (O와 같은) 원소를 막 매트릭스에 제공할 수 있고, 막 매트릭스의 일부가 될 수 있다. 용어 "불활성 가스"는 RF 전력이 인가될 경우 전구체를 여기시키는 플라즈마 발생 가스를 지칭하나, 반응물과는 달리 막 매트릭스의 일부가 되지는 않는다.
일부 구현예에서, "단층"은 하나의 분자 두께 층을 지칭하고, "하위층"은, 반드시 단층이 아니지만 최종 막의 하위 단위 부분으로서 ALD의 한 사이클에 증착된 층을 지칭한다. 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, 표시된 변수의 임의의 값은 ("약"의 표시 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 의미는 일부 구현예에서 반드시 보통의 그리고 관습적인 의미를 배제하는 것은 아니다.
본 개시에서, "연속적으로"는, 진공 파괴가 없으며, 시간적으로 중단이 없고, 임의의 물질의 개입 단계가 없으며, 다음 단계로서 그 직후에 처리 조건의 변경이 없고, 또는 일부 구현예에서는 두 개의 구조물 사이에 두 개의 구조물 이외의 분리된 물리적 또는 화학적 구조물이 개입하지 않음을 지칭한다.
본 개시에서, "단차" 또는 "오목부"는, 기판 상에 형성된 상부 표면, 측벽, 및 하부 표면을 갖는 임의의 구조를 지칭하며, 이는 높이 방향으로 직렬로 배열될 수 있거나 단일 단차일 수 있고, 트렌치, 비아, 또는 다른 오목부를 구성할 수 있다. 또한, 본 개시에서, 트렌치는 홀/비아를 포함한 임의의 오목부 패턴이고, 이는 일부 구현예에서, 10 내지 50 nm(전형적으로는 15 내지 30 nm)의 폭(여기서 상기 트렌치가 상기 폭과 실질적으로 동일한 길이를 갖는 경우, 상기 트렌치는 홀/비아로 지칭되고, 그의 직경은 10 내지 50 nm이다), 30 내지 200 nm(전형적으로 50 내지 150 nm)의 깊이, 및 3 내지 20(전형적으로 3 내지 10)의 종횡비를 갖는다.
본 개시에서, SiO 막은, 공정 레시피에 따라 SiO 막뿐만 아니라 SiOC 막, SiON 막, SiOCN 막 등을 포함하며, 달리 설명하지 않는 한 막의 이름은 비화학양론적 방식으로 단지 막 유형(주요 구성 원소에 의해 단순히 나타남)을 지칭하는 약어이다.
도 2는, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하는 반면에 흰색의 셀은 오프 상태를 표시하고, 각 열의 폭이 각 공정의 지속 시간을 표시하는 것은 아니다. 제1 단계("공급")는 BDEAS를 펄스로 반응 공간에 공급하는 단계 및 반응 공간 내 BDEAS의 열분해를 실질적으로 억제하는 분위기에서 400°C 초과(바람직하게는 500°C 초과 650°C 미만)의 온도를 갖는 서셉터 상에 배치된 기판 상에 BDEAS를 흡착시키는 단계를 포함한다. 일반적으로, 온도가 높을수록, BDEAS의 열분해가 상기 분위기에서 충분히 또는 실질적으로 억제될 수 있는 한, 특히 트렌치의 측벽 및 하부에서 최종 생성된 실리콘 산화물 막의 막 품질이 더욱 향상되는 것을 기대할 수 있다. 바람직하게, 분위기는 1,000 Pa 이하의 압력(더욱 바람직하게는 400 Pa 이하, 예를 들어 333 Pa 내지 400 Pa)과 5% 내지 70%의 산소 농도(보다 바람직하게는 30% 내지 60%의 산소 농도)를 가지며, 따라서 증착 온도가 높은 경우이더라도 BDEAS의 열분해는 억제될 수 있다. 일부 구현예에서, 산화제로서 산소는 400 sccm 내지 5600 sccm(바람직하게는 1600 sccm 내지 4000 sccm)의 유량으로 반응 공간에 공급되고, 하나 이상의 불활성 가스(예, Ar 및/또는 He와 같은 희귀 가스)는 400 sccm 내지 5600 sccm(바람직하게는 2000 sccm 내지 4400 sccm)의 유량으로 공급된다. 산화제로서, 이산화질소가 또한 사용될 수 있다. 이 구현예에서, 산화제는 증착 사이클 전체에 걸쳐 연속적으로 공급된다. "공급" 단계에서, 2000 sccm의 유량으로 공급된 희귀 가스(예, Ar 및/또는 He)와 같은 불활성 가스인 캐리어 가스의 흐름을 사용하여 BDEAS를 공급한다. ALD는 자기-제한 흡착 반응 공정이기 때문에, 증착된 전구체 분자의 양은 반응성 표면 사이트의 개수에 의해 결정되며 포화 후 전구체의 노출과는 무관하고, 전구체의 공급은 사이클마다 이에 의해 반응성 표면 사이트가 포화되도록 한다("화학 흡착"은 화학적 포화 흡착을 지칭함). 이 구현예에서, 캐리어 가스는 증착 사이클 전체에 걸쳐 연속적으로 공급된다.
캐리어 가스의 연속적인 흐름은 유동 통과 시스템(FPS)을 이용하여 달성될 수 있되, 캐리어 가스 라인은 전구체 리저버(용기)를 갖는 우회 라인을 구비하고, 메인 라인과 우회 라인이 스위칭되되, 캐리어 가스만을 반응 챔버에 공급하고자 하는 경우에 우회 라인은 닫히고, 반면 캐리어 가스와 전구체 가스 모두를 반응 챔버에 공급하고자 하는 경우에 메인 라인은 닫히게 되고 캐리어 가스는 우회 라인을 통해 흐르며 전구체 가스와 함께 용기로부터 흘러 나온다. 이 방식으로, 캐리어 가스는 반응 챔버 내로 연속해서 흐를 수 있고, 메인 라인과 우회 라인 사이를 스위칭함으로써 전구체 가스를 펄스로 운반할 수 있다. 도 1b는 본 발명의 구현예에 따른 유동 통과 시스템(FPS)을 사용하는 전구체 공급 시스템을 도시한다(검은색 밸브는 밸브가 닫혔음을 표시함). 도 1b의 (a)에 나타낸 바와 같이, 전구체를 반응 챔버(미도시)에 공급하는 경우에 우선, Ar(또는 He) 같은 캐리어 가스가 밸브(b 및 c)를 갖는 가스 라인을 통해 흐른 다음 용기(리저버)(20)로 진입한다. 캐리어 가스는 용기(20) 내부의 증기압에 대응하는 양으로 전구체 가스를 운반하면서 용기(20)로부터 흘러 나오고, 밸브(f 및 e)를 갖는 가스 라인을 통해 흐른 다음 전구체와 함께 반응 챔버에 공급된다. 위에서, 밸브(a) 및 밸브(d)는 닫힌다. 캐리어 가스(귀가스)만을 반응 챔버에 공급할 경우, 도 1b의 (b)에 나타낸 바와 같이, 캐리어 가스는 용기(20)를 우회하며 밸브(a)를 갖는 가스 라인을 통해 흐른다. 위에서, 밸브(b, c, d, e, 및 f)는 닫힌다.
일부 구현예에서, "공급"의 지속 시간은 0.1 초 내지 3.0 초(바람직하게는 0.2 초 내지 0.5 초)이다.
다음으로, 제2 단계("퍼지-1")에서, 반응 공간은 기판 표면으로부터 과량의 BDEAS 및 비흡착된 BDEAS를 제거하기 위해 퍼지된다. 퍼지는, 퍼지 가스로서 기능하는 산화제 및 캐리어 가스의 연속 흐름에 의해 간단히 이루어질 수 있지만, 별도의 퍼지 가스를 사용할 수 있다. 일부 구현예에서, 퍼지의 지속 시간은 0.2 초 내지 2.0 초(바람직하게는 0.3 초 내지 1.0 초)이다. 일부 구현예에서, PEALD에서, 퍼지 지속 시간을 (예를 들어, 0.1 초 내지 0.5 초의 범위까지) 단축함으로써, 일부 비흡착된 BDEAS는 상부 표면과 트렌치에 남아 있을 수 있고, 이는 어느 정도 측벽 상에서의 막 품질을 개선하면서 트렌치의 상부 표면과 하부에서의 막 품질을 낮출 수 있다. 이는 더 짧은 퍼지 지속 시간이 트렌치에서 더 많은 BDEAS를 남기기 때문일 수 있고, 이는 구름처럼 트렌치에 머무를 수 있고, 플라즈마가 하부에 도달하는 것을 부분적으로 차단할 수 있으면서 더 많은 플라즈마 에너지가 측벽에 도달한다.
다음으로, 제3 단계("RF 펄스")에서, 기판 표면 상에 흡착된 BDEAS는 산소 플라즈마에 노출됨으로써, 기판 상에 실리콘 산화물 단층 또는 하위층을 증착한다. 일부 구현예에서, RF 전력 인가 기간(플라즈마에 노출되는 기간)은 0.2 초 내지 2.0 초(바람직하게는 0.2 초 내지 1.2 초)의 범위이다. 플라즈마 노출 시간은, 전도성으로 결합된 평행 전극이 사용되는 경우에 상부 및 하부 전극 사이의 거리를 변화시킴으로써 또한 조절될 수 있되, 상기 거리를 증가시킴으로써, 상기 반응 공간 내로 진입하는 전구체의 유량이 일정한 경우에 상기 전구체가 상기 상부 전극과 상기 하부 전극 사이의 반응 공간에 유지되는 유지 시간이 연장될 수 있다. 일부 구현예에서, 상부 전극과 하부 전극 사이의 거리(mm)는 7.5 mm 내지 13 mm(바람직하게는 7.5 mm 내지 10 mm)이다. 일부 구현예에서, 증착을 위한 RF 전력(W)(예, 13.56 MHz)은 300 mm 웨이퍼에 대해 측정된 바와 같이 50 W 내지 1000 W(바람직하게는 200 W 내지 500 W)이고, 이는 다양한 크기의 웨이퍼를 위해 W/cm2의 단위로 변환될 수 있다.
제3 단계 후, 제4 단계("퍼지-2")에서, 반응 공간은, 미반응된 BDEAS 및 반응 부산물을 기판의 표면으로부터 제거하기 위해 퍼지된다. 퍼지는, 퍼지 가스로서 기능하는 산화제 및 캐리어 가스의 연속 흐름에 의해 간단히 이루어질 수 있지만, 별도의 퍼지 가스를 사용할 수 있다. 일부 구현예에서, 퍼지의 지속 시간은 0.1 초 내지 1.0 초(바람직하게는 0.1 초 내지 0.3 초)이다.
공정 사이클은, 예를 들어 도 1a에 나타낸 장치를 포함한 임의의 적절한 장치를 사용하여 수행될 수 있다. 도 1a는, 본 발명의 일부 구현예에 사용될 수 있고 바람직하게는 아래에 설명되는 시퀀스를 수행하기 위해 프로그래밍된 제어부와 협력하는 PEALD 장치의 개략도이다. 이 도면에서, 서로 마주하며 평행한 한 쌍의 전기 전도성 평판 전극(4, 2)을 반응 챔버(3)의 내부(반응 구역)(11)에 공급하고, HRF 전력(13.56 MHz 또는 27 MHz)(25)을 일측에 인가하고 타측(12)을 전기적으로 접지시킴으로써, 플라즈마가 전극들 사이에서 여기된다. 온도 조절기가 하부 스테이지(하부 전극)(2)에 제공되어, 그 위에 놓인 기판(1)의 온도는 주어진 온도로 일정하게 유지된다. 상부 전극(4)은 샤워 플레이트로서의 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 챔버로부터 이송되는 게이트 밸브는 본 도면에서 생략됨). 이송 챔버는 또한 배기 라인(6)을 구비한다. 일부 구현예에서, 다중 원소 막의 증착 및 표면 처리는 동일한 반응 공간에서 수행되어, 모든 단계들은 기판을 공기 또는 다른 산소 함유 대기에 노출시키지 않고 연속적으로 수행될 수 있다.
일부 구현예에서, 도 1a에 도시된 장치에서는, 도 1b에 나타낸(앞에서 설명된) 불활성 가스의 흐름 및 전구체 가스의 흐름을 스위칭하는 시스템이, 반응 챔버의 압력을 요동시키지 않고 전구체 가스를 펄스로 유입하기 위해 사용될 수 있다.
당업자는 본 장치가 본원의 다른 곳에서 기술된 증착 공정 및 반응기 세정 공정의 수행이 일어나도록 프로그래밍되었거나 달리 구성된 하나 이상의 제어기(들)(미도시)를 포함함을 이해할 것이다. 제어기(들)는, 당업자가 이해하는 바와 같이, 다양한 전력원, 가열 시스템, 펌프, 로보틱스, 및 반응기의 가스 흐름 제어기 또는 밸브들과 통신한다.
일부 구현예에서, 듀얼 챔버 반응기(서로 근접하게 배치된 웨이퍼를 처리하기 위한 2개의 섹션 또는 컴파트먼트)가 사용될 수 있고, 반응물 가스 및 귀가스는 공유된 라인을 통해 공급될 수 있는 반면, 전구체 가스는 공유되지 않는 라인을 통해 공급된다.
충진 능력을 갖는 막은, 3D 교차점 메모리 소자에서의 셀 분리, 자기 정렬 비아, (현재의 폴리실리콘을 대체하는) 더미 게이트, 리버스 톤 패터닝, PC RAM 분리, 절단된 하드 마스크, 및 DRAM 스토리지 노드 콘택(SNC) 분리를 포함하되 이에 제한되지 않는 반도체 소자에 다양하게 적용될 수 있다.
실시예
조건 및/또는 구조가 명시되지 않은 다음 실시예에 있어서, 당업자는 본 개시를 고려하여 일상적인 실험의 일환으로 이러한 조건 및/또는 구조를 쉽게 제공할 수 있다. 당업자는 실시예에 사용된 상기 장치가 본원의 다른 곳에서 설명된 증착 공정 및 반응기 세정 공정의 수행을 유도하도록 프로그래밍되었거나 달리 구성된 하나 이상의 제어기(들)(미도시)를 포함하였음을 이해할 것이다. 제어기(들)를, 당업자가 이해하는 바와 같이, 다양한 전력원, 가열 시스템, 펌프, 로보틱스, 및 반응기의 가스 유량 제어기 또는 밸브들과 통신시켰다.
참조예 1 (BDEAS의 열 안정성)
참조예 1에서, BDEAS의 열 안정성을 시험하기 위해, 1.20 nm의 두께를 갖는 원래 또는 자연 산화물 막이 위에 형성된 Si 기판을, 도 1b에 나타낸 가스 공급 시스템(FPS)을 이용해 도 1a에 나타낸 장치 내에 배치하였다. 반응 챔버의 대기는, RF 전력을 반응 챔버에 인가하지 않고 400 Pa의 압력 하에서 2000 sccm의 BDEAS 및 2000 sccm의 산소를 공급함으로써 제어되었고, 서셉터 온도는 400°C 내지 650°C 범위 내에서 설정되었고, 서셉터 온도가 설정 온도에 도달한 후 800 초에서, 막의 두께를 각각의 설정 온도에서 측정하였다. 비교 참조예로서, BDEAS가 반응 챔버에 공급되지 않았음을 제외하고 참조예 1과 동일한 방식으로 각각의 설정 온도에서 막의 두께를 측정하였다.
도 3은, 막 두께와 서셉터 온도 사이의 개략적인 관계를 표시한 그래프를 나타낸다. 도 3에 나타낸 바와 같이, BDEAS 공급("공급 있음")을 갖는 막의 두께 및 BDEAS 공급이 없는("공급 없음") 막의 두께는 전체 온도 범위에서 실질적으로 동일하였다. 막의 두께는, BDEAS가 공급되지 않은 경우에도 온도가 증가함에 따라 증가하는 것으로 나타났고, 이는 (아래의 자연 산화물 막을 갖는) 기판 자체가 산소에 의해 더 산화되어 겉보기 두께를 증가시키기 때문임을 유의해야 한다. 또한, BDEAS가 550°C, 600°C, 및 650°C의 온도에서 공급되지 않은 경우보다 BDEAS가 공급되었을 경우에 막 두께는 약간 컸다. 이는 BDEAS가 열에 의해 기판 표면에 흡착되었기 때문이다. BDEAS가 설정된 온도에서 열분해되면, 분해된 구성 요소(예, 아민, 탄소의 산화물, 질소의 산화물, 및 실리콘의 산화물)가 기판 표면 상에 연속적으로 축적되어, 특히 더 높은 온도에서 막 두께를 상당히 증가시킨다. 따라서, 도 3에 나타낸 결과는 BDEAS가 400°C 내지 650°C의 온도 범위에서 열분해되지 않음을 확인한다.
실시예 1 (높은 증착 온도에서의 막 품질 개선)
도 1a에 나타낸 장치 및 도 1b에 나타낸 가스 공급 시스템(FPS)을 사용하여 도 2에 나타낸 공정 시퀀스에서 하기 표 1에 나타낸 조건(증착 온도 변화) 하에, 막의 막 품질을 결정하기 위해 PEALD 공정으로, 약 30 nm의 개구와 약 90 nm의 깊이를 갖는 트렌치(종횡비는 대략 3임)를 갖는 Si 기판(300 mm의 직경 및 0.7 mm의 두께를 갖음) 상에 실리콘 산화물 막을 증착하였다. 실리콘 산화물 막의 증착이 완료된 후, 트렌치를 갖는 각각의 기판의 단면도를 STEM을 사용하여 사진을 찍었다.
표 1(수치는 근사치임)
각각의 실리콘 산화물 막의 증착이 완료된 후(상부 표면 상에서 25 nm의 평균 막 두께를 갖음), 기판은 (22°C에서 30 초 동안 1%의 농도를 갖는 dHF의 용액에 기판을 담금으로써) 습식 식각을 하였다. 또한, 습식 식각 후에 트렌치를 갖는 각각의 기판의 단면도를 STEM을 사용하여 사진을 찍었다.
도 4는 상이한 온도에서 실리콘 산화물 막의 증착("증착 상태") 다음에 습식 식각("DHF 침지후")을 거친 트렌치 단면의 STEM 사진을 보여주는 차트이다. 도 4에서, "측면/상부 [%]"는 증착된 경우의 상부 두께에 대한 측벽 두께의 비율 [%]을 지칭하고, "WERR [TOX 비]"는 표준 써멀 산화물 막의 습식 식각 속도에 대해 각 부분의 습식 식각 속도를 지칭한다. 도 4에 나타낸 바와 같이, 증착 온도가 400°C 이상, 특히 500°C(더욱 바람직하게는 550°C 이상)이었을 경우, 측벽 부분의 막 품질이 개선되었다.
실시예 2 (다른 파라미터를 이용한 막 품질의 개선)
하기 표 2에 나타낸 조건을 제외하고는 실시예 1과 동일한 방식으로 실리콘 산화물 막을 Si 기판 상에 증착하였다.
표 2(수치는 근사치임)
각각의 실리콘 산화물 막의 증착 완료 후, 기판은 실시예 1과 동일한 방식으로 습식 식각을 하였다. 또한, 습식 식각 후에 트렌치를 갖는 각각의 기판의 단면도를 STEM을 사용하여 사진을 찍었다. UHT-9에서 증착 압력이 3,000 Pa였을 경우, 막 증착은 매우 비정상적이어서, 이 샘플의 습식 식각 평가가 수행되지 않았음을 유의해야 한다.
도 5는 상이한 압력, 상이한 산소 농도, 및 상이한 퍼지 지속 시간에서 실리콘 산화물 막의 증착("증착 상태") 다음에 습식 식각("DHF 침지후")을 거친 트렌치 단면도의 STEM 사진을 보여주는 차트이다. 도 5에서, "측면/상부 [%] 및 "WERR [TOX 비]"는 도 4에서와 동일한 의미를 나타낸다. 도 5에 나타난 바와 같이, 높은 증착 온도(650°C)에서, UHT-7에서 증착 압력이 400 Pa인 경우, UHT-8(1,000 Pa)과 비교한 바와 같이, 측벽 부분의 막 품질이 개선되었다. 그러나, 상부의 막 품질은, UHT-8(1,000 Pa)과 비교한 바와 같이, UHT-7의 400 Pa의 압력에서 개선되지 않았고, 하부의 막 품질은, UHT-8(1,000 Pa)과 비교한 바와 같이, UHT-7의 400 Pa의 압력에서 악화되었다. 이는, 각 부분의 표면에 의해 수용된 플라즈마 충돌이 상부(400 Pa) > 상부(1000 Pa) > 하부(400 Pa) > 하부(1000 Pa) > 측면(400 Pa) > 측면(1000 Pa)의 순서이고 하부(1000 Pa) 주위에서 막품질을 증가시키기 위한 최적 플라즈마 충돌이 있기 때문일 수 있고, 플라즈마 충돌이 최적의 플라즈마 충돌보다 높거나 낮을 경우, 막 품질은 도 7에 개략적으로 나타낸 바와 같이 덜 개선될 수 있다. 플라즈마는 높은 자유 전자 함량(약 50%)을 갖는 부분적으로 이온화된 가스이고, 평행한 전극 사이에 AC 전압을 인가함으로써 플라즈마가 여기되는 경우, 플라즈마 시스와 하부 전극 사이에서 발달된 자기 dc 바이어스(VDC)에 의해 가속되어 상기 하부 전극 위에 놓인 막에 상기 막에 수직한 방향(이온 입사 방향)으로 충돌한다. 이러한 비제한적인 이론에 기초하여, 당업자는 증착 압력을 조절함으로써 각 부분의 막 품질을 조정할 수 있다(이렇게 함으로써, 하부 부분의 막 품질과 측벽 부분의 것 (그리고 추가적으로 상부 부분의 것)이 실질적으로 동일한 수준으로 조절될 수 있음). 플라즈마의 충돌은 플라즈마 밀도(플라즈마 활성 종의 양) 또는 이온의 운동 에너지로 나타낼 수 있고, 플라즈마 밀도는 미국 특허 공보 제2017/0250068호에 개시된 바와 같이 평가될 수 있으며, 그 개시 내용은 그 전체가 본원에 참조로 포함된다.
도 5에 나타낸 바와 같이, 높은 증착 온도(650℃)에서, 산화제 가스(이 구현예에서 산소 + 아르곤) 중의 산소 농도가 UHT-6의 50%인 경우, UHT-10(5%) 및 UHT-11(70%)과 비교한 바와 같이, 측벽 부분의 막 품질이 개선되었다. 그러나, UHT-10(5%) 및 UHT-11(70%)과 비교한 바와 같이, 상부의 막 품질이 UHT-6의 50%의 산소 농도에서 악화되었다. 이는, 산소 플라즈마뿐만 아니라 아르곤 플라즈마도 측벽 부분의 막 품질에 기여할 수 있기 때문이고, 산소 농도와 아르곤 농도의 비가 대략 동일한(예, ±10%, 즉, 40% 내지 60%) 경우, 측벽 부분의 막 품질은 상당히 개선될 수 있다. 이러한 비제한적인 이론에 기초하여, 당업자는 산소 농도를 조절함으로써 원하는 각 부분의 막 품질을 조절할 수 있을 것이다.
또한, 도 5에 나타낸 바와 같이, 높은 증착 온도(650°C)에서, 퍼지 지속 시간이 UHT-6의 0.3 초였을 경우, UHT-7(2.0 초)과 비교한 바와 같이, 측벽 부분의 막 품질이 개선되었다. 그러나, UHT-7(2.0초)과 비교한 바와 같이, 상부의 막 품질과 하부의 막 품질은, UHT-6의 0.3 초의 퍼지 지속 시간에서 악화되었다. 이는, 일부 비흡착된 BDEAS가 0.3 초의 퍼지 지속 시간에서 상부 표면 및 트렌치 내에 남아 있을 수 있기 때문이고, 이는 측벽 부분의 막 품질을 특정한 정도로 개선하면서, 상부의 막 품질 및 하부의 막 품질을 낮출 수 있다. 이는 더 짧은 퍼지 지속 시간이 트렌치에서 더 많은 BDEAS를 남기기 때문일 수 있고, 이는 구름처럼 트렌치에 머무를 수 있고, 플라즈마가 하부에 도달하는 것을 부분적으로 차단할 수 있으면서 더 많은 플라즈마 에너지가 측벽에 도달한다. 이러한 비제한적인 이론에 기초하여, 당업자는 산소 농도를 조절함으로써 원하는 각 부분의 막 품질을 조절할 수 있을 것이다.
실시예 3 (막 품질 개선 - 블랭킷 증착)
실리콘 산화물 막을, 이것이 블랭킷 증착(패턴 증착이 아님)이라는 점을 제외하고, 실시예 1에서와 동일한 방식으로 트렌치 없는 Si 기판 상에 증착하였다.
각각의 실리콘 산화물 막의 증착 완료 후, 기판은 실시예 1과 동일한 방식으로 습식 식각을 하였다. 또한, 습식 식각 후, 각각의 실리콘 산화물 막의 막 특성을 평균 두께, 평면 내 두께 균일성, 및 습식 식각 속도의 측면에서 평가하였다.
도 6은, 도 4에 나타낸 증착에서 사용된 증착 조건과 최종 생성된 실리콘 산화물 막의 막 특성을 나타낸 차트이고, 막의 2D 컬러 맵 분석에 의해 박막 두께 프로파일 측정 이미지의 컬러 버전을 포함한다. 도 6에서, "제1 WERR/TOX"는 습식 식각의 처음 1분 동안 측정된 표준 써멀 산화물 막의 습식 식각 속도에 대해 각각의 막의 습식 식각 속도를 지칭하는 한편, "제2 WERR/TOX"는, 습식 식각의 두 번째 1분 동안 측정된, 표준 써멀 산화물 막의 습식 식각 속도에 대해 각 막의 습식 식각 속도를 지칭한다. 도 6에 나타난 바와 같이, 높은 증착 온도(650°C)에서, UHT-9에서 증착 압력이 3,000 Pa인 경우, UHT-6, -7, 및 -8(400 Pa)에서와 비교한 바와 같이, 막 증착은 매우 비정상적이었고 막 품질이 평가되지 않았다. 또한, UHT-6 및 -7(400 Pa)에서와 비교한 바와 같이, 증착 압력이 UHT-8의 1,000 Pa인 경우, 정상 증착이라 하더라도, 막 품질은 악화되었다. 또한, 도 6에 나타낸 바와 같이, 5% 내지 70%의 산소 농도는 적절한 막 품질을 제공하기 위한 실행 가능한 범위였다.
당업자는 본 발명의 사상을 벗어나지 않고, 다수의 그리고 다양한 변형이 이루어질 수 있음을 이해할 것이다. 따라서, 본 발명의 형태는 단지 예시적인 것이며 본 발명의 범주를 한정하도록 의도된 것이 아니라는 것을 분명히 이해해야 한다.
Claims (9)
- 플라즈마 강화 원자층 증착(PEALD)에 의해 반응 공간 내의 기판 상에 비스(디에틸아미노)실란(BDEAS)을 사용하여 실리콘 산화물 막을 증착하는 방법으로서, PEALD의 반복하는 증착 사이클 각각은,
(i) 상기 반응 공간에서 BDEAS의 열분해를 실질적으로 억제하는 분위기에서 400℃ 초과의 온도를 갖는 서셉터 상에 배치된 상기 기판 상에 BDEAS를 흡착시키는 단계; 및
(ii) BDEAS가 위에 흡착된 상기 기판을 상기 반응 공간의 대기에서 산소 플라즈마에 노출시킴으로써 상기 실리콘 산화물 막의 단층 또는 하위층을 증착하는 단계를 포함하는, 방법. - 제1항에 있어서, 상기 서셉터의 온도는 650°C 이하인, 방법.
- 제1항에 있어서, 상기 분위기는 1,000 Pa 이하의 압력과 5% 내지 70%의 산소 농도를 갖는, 방법.
- 제3항에 있어서, 상기 분위기는 400 Pa 이하의 압력을 갖는, 방법.
- 제3항에 있어서, 상기 분위기는 30% 내지 60%의 산소 농도를 갖는, 방법.
- 제1항에 있어서, 반복하는 증착 사이클 각각은, 단계 (i)과 단계 (ii) 사이에 상기 반응 공간을 퍼지하는 단계를 추가로 포함하는, 방법.
- 제6항에 있어서, 상기 퍼지 단계는 2.0 초 미만 동안 수행되는, 방법.
- 제1항에 있어서, 상기 기판은 패터닝된 단차를 갖고, 그 위에 단계 (i)에서 BDEAS가 흡착되는, 방법.
- 제8항에 있어서, 상기 패터닝된 단차는 3 이상의 종횡비를 갖는 트렌치인, 방법.
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TW202145344A (zh) | 2020-04-08 | 2021-12-01 | 荷蘭商Asm Ip私人控股有限公司 | 用於選擇性蝕刻氧化矽膜之設備及方法 |
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KR20210127620A (ko) | 2020-04-13 | 2021-10-22 | 에이에스엠 아이피 홀딩 비.브이. | 질소 함유 탄소 막을 형성하는 방법 및 이를 수행하기 위한 시스템 |
US11821078B2 (en) | 2020-04-15 | 2023-11-21 | Asm Ip Holding B.V. | Method for forming precoat film and method for forming silicon-containing film |
KR20210128343A (ko) | 2020-04-15 | 2021-10-26 | 에이에스엠 아이피 홀딩 비.브이. | 크롬 나이트라이드 층을 형성하는 방법 및 크롬 나이트라이드 층을 포함하는 구조 |
US11996289B2 (en) | 2020-04-16 | 2024-05-28 | Asm Ip Holding B.V. | Methods of forming structures including silicon germanium and silicon layers, devices formed using the methods, and systems for performing the methods |
TW202140846A (zh) | 2020-04-17 | 2021-11-01 | 荷蘭商Asm Ip私人控股有限公司 | 注入器、及垂直熔爐 |
KR20210130646A (ko) | 2020-04-21 | 2021-11-01 | 에이에스엠 아이피 홀딩 비.브이. | 기판을 처리하기 위한 방법 |
-
2020
- 2020-08-10 KR KR1020200099891A patent/KR20210024420A/ko unknown
- 2020-08-18 TW TW109128053A patent/TWI838570B/zh active
- 2020-08-21 US US16/999,065 patent/US11527400B2/en active Active
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2022
- 2022-12-08 US US18/077,280 patent/US12033849B2/en active Active
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TWI838570B (zh) | 2024-04-11 |
US11527400B2 (en) | 2022-12-13 |
US12033849B2 (en) | 2024-07-09 |
US20230112490A1 (en) | 2023-04-13 |
US20210057214A1 (en) | 2021-02-25 |
TW202108806A (zh) | 2021-03-01 |
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