KR20180092881A - 열적 ald 및 peald로 산화막을 증착하기 위한 방법 - Google Patents
열적 ald 및 peald로 산화막을 증착하기 위한 방법 Download PDFInfo
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- KR20180092881A KR20180092881A KR1020180015817A KR20180015817A KR20180092881A KR 20180092881 A KR20180092881 A KR 20180092881A KR 1020180015817 A KR1020180015817 A KR 1020180015817A KR 20180015817 A KR20180015817 A KR 20180015817A KR 20180092881 A KR20180092881 A KR 20180092881A
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- Prior art keywords
- gas
- reaction chamber
- peald
- oxide film
- thermal ald
- Prior art date
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Abstract
열적 ALD 및 PEALD에 의해 기판 상에 산화물 막을 퇴적하는 방법은, 반응 챔버 내에 기판을 제공하는 단계; 상기 반응 챔버에서 열적 ALD에 의해 상기 기판 상에 제1 산화물 막을 퇴적하는 단계; 및 진공을 파괴하지 않고, 상기 반응 챔버 내에서 PEALD에 의해 상기 제1 산화물 막 상에 제2 산화물 막을 연속적으로 퇴적시키는 단계를 포함한다.
Description
본 발명은 일반적으로 열적 원자층 증착(열적 ALD) 및 플라즈마 강화 원자층 증착(PEALD)으로 산화막을 증착하기 위한 방법에 관한 것이다.
반도체 소자들의 최소화가 진전됨에 따라, 반도체 제조 공정 동안 야기되는 리세스 패턴 또는 하부층에 대한 손상은 더욱 문제가 된다. 이는, 소자들이 최소화 될 때 리세스 패턴 또는 하부층에 대한 손상에 의해 야기되는 치수 변화가 패터닝 정밀도에 더 큰 영향을 미쳐서 기능 저하로 이어지기 때문이다. 종래에, SiO 막은 패터닝을 위해 또는 기능성 막으로서 사용된다; 그러나, 직접적인 플라즈마를 사용하는 PEALD, 즉 용량성 결합 플라즈마(CCP)는 리세스 패턴 또는 하부층에 대한 손상을 야기하고, 손상 정도는 플라즈마 출력에 따라 달라지는 경향이 있어서, 최소화된 반도체 소자들을 제조하기 위해서는 낮은 출력이 사용되었다. 특히, 산화에 대하여 낮은 저항성을 갖는 탄소계 하부층들의 경우, 하부층에 대한 손상을 최소화하기 위해 통상적으로 낮은 RF 출력의 적용이 사용된다. 관례적으로 손상이 막의 수축으로 표시될 때, 하부막은 전형적으로 약 2 내지 5%의 수축을 보여준다. 그러나, 최소화된 소자에서 막의 수축을 줄이고자 하는 요구가 높아지고 있다.
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 구현예에서, 산화막은 연속적인 2단계 공정을 사용하여 형성되고, 상기 2단계 공정은 기판의 하부층이 플라즈마에 노출되는 것을 피함으로써 치수 열화 및/또는 하부층의 산화를 방지하도록 제1 단계로서 열적 ALD를 제2 단계로서 PEALD를 포함한다. 일부 구현예에서, 제1 단계 및 제2 단계는 동일 반응 챔버에서 연속적으로 수행된다. 일부 구현예에서, 반응물이 비여기 상태에 있을 때조차 열적 ALD를 위한 반응물 및 전구체의 반응도는 PEALD에 대한 것보다 높기 때문에, 열적 ALD를 위한 반응물은 PEALD를 위한 반응물과 상이한 유동 경로를 통해 반응 챔버에 공급된다. 열적 ALD를 위한 전구체는 PEALD를 위한 전구체와 상이할 수 있거나 상이하지 않을 수 있다.
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 1a는 본 발명의 구현예에 사용할 수 있는 산화막을 증착하기 위한 열적 ALD 및 플라즈마 강화 ALD(plasma-enhanced atomic layer deposition, PEALD)의 개략적인 표시이다.
도1b는 본 발명의 구현예에 사용할 수 있는 유동 통과 시스템(flow-pass system, FPS)을 사용하는 전구체 공급 시스템의 개략적인 표시를 도시하고, 여기서 (a)는 캐리어 가스가 전구체를 거기로부터 반송하기 위해 병을 통해 흐르는 상태를 표시하고, (b)는 캐리어 가스가 병을 우회하는 상태를 표시한다.
도 2는, 본 발명의 구현예에 따른 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 3은, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스와 조합된 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 4는, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 5는, 본 발명의 구현예에 따른 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 6은, 본 발명의 다른 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스와 조합된 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 7은 본 발명의 다른 구현예에 사용할 수 있는 산화막을 증착하기 위한 열적 ALD 및 플라즈마 강화 ALD(PEALD)의 개략적인 표시이다.
도 1a는 본 발명의 구현예에 사용할 수 있는 산화막을 증착하기 위한 열적 ALD 및 플라즈마 강화 ALD(plasma-enhanced atomic layer deposition, PEALD)의 개략적인 표시이다.
도1b는 본 발명의 구현예에 사용할 수 있는 유동 통과 시스템(flow-pass system, FPS)을 사용하는 전구체 공급 시스템의 개략적인 표시를 도시하고, 여기서 (a)는 캐리어 가스가 전구체를 거기로부터 반송하기 위해 병을 통해 흐르는 상태를 표시하고, (b)는 캐리어 가스가 병을 우회하는 상태를 표시한다.
도 2는, 본 발명의 구현예에 따른 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 3은, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스와 조합된 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 4는, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 5는, 본 발명의 구현예에 따른 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 6은, 본 발명의 다른 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스와 조합된 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다.
도 7은 본 발명의 다른 구현예에 사용할 수 있는 산화막을 증착하기 위한 열적 ALD 및 플라즈마 강화 ALD(PEALD)의 개략적인 표시이다.
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, 샤워 헤드 또는 다른 포트를 통해 공정 챔버에 유입되는 공정 가스는 실리콘 함유 전구체 또는 금속 함유 전구체 및 첨가 가스로 구성되거나, 본질적으로 이루어지거나, 또는 이루어질 수 있다. 첨가 가스는, RF 전력이 첨가 가스에 인가될 때, 전구체를 산화시키기 위한 반응물 가스 및 전구체를 여기시키기 위한 불활성 가스(예를 들면, 비활성 가스)를 포함할 수 있다. 불활성 가스는 캐리어 가스 및/또는 희석 가스로서 반응 챔버에 투입될 수 있다. 전구체 및 첨가 가스는 혼합 가스로서 또는 개별적으로 반응 공간에 유입될 수 있다. 전구체는 비활성 가스와 같은 캐리어 가스와 함께 유입될 수 있다. 공정 가스 이외의 가스, 즉 샤워 헤드를 통과하지 않고 유입되는 가스는, 예를 들면 반응 공간을 씰링하기 위해 사용될 수 있고, 비활성 가스와 같은 씰(seal) 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 인가될 때 원소(예컨대, O)를 막 매트릭스에 제공할 수 있고, 막 매트릭스의 일부가 될 수 있다. 용어 "불활성 가스"는 RF 전력이 인가될 때 전구체를 여기시키는 가스를 지칭하나, 반응물과는 달리 막 매트릭스의 일부가 되지는 않는다.
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.
구현예에서, 열적 ALD 및 PEALD로 기판 상에 산화막을 증착하기 위한 방법은 반응 챔버 내에 기판을 제공하는 단계; 상기 반응 챔버 내에서 열적 ALD로 상기 기판 상에 제1 산화막을 증착하는 단계; 및 진공을 깨뜨리지 않고서 상기 반응 챔버 내에서 상기 제1 산화막 상에 제2 산화막을 연속적으로 증착하는 단계를 포함한다.
상기에서, 단어 "연속적으로"는 다음 중 적어도 하나를 지칭한다: 구현예에 따라, 공간에서의 중단 없이(예컨대, 기판을 이동시키지 않고서), 유동에서의 중단 없이(예컨대, 적어도 하나의 중단 없는 유입), 분위기에 노출 없이, 및 임의의 물질 개재 단계 없이(퍼징 또는 다른 무시할 수 있는 단계와 같은 보조 단계는 제외). 본 개시에서, "연속적인" 유동은 일정한 유속(대안적으로, 비록 유동이 "연속적"일지라도, 유속은 시간에 따라 변할 수 있음)을 가진다.
일부 구현예에서, 반응물로서, H2O 또는 OH기를 함유하는 가스가 열적 ALD를 위해 사용될 수 있기 때문에, 잔류 수분은 반응 챔버 내에 남을 수 있으므로, 반응 챔버 내 수분의 분압을 감소시키기 위해, 열적 ALD와 PEALD의 연속성을 유지하면서 열적 ALD와 PEALD 사이에서 H2와 같은 환원 가스를 사용하여 반응 챔버로부터 잔류 수분을 제거할 수 있다.
제1 산화막은 플라즈마에 노출되지 않고서 열적 ALD에 의해 기판의 하부층 상에 증착되기 때문에, 하부층에 대한 손상이 효과적으로 억제될 수 있다; 예컨대, 패터닝을 위해 사용되는 하부층으로서 탄소 함유막(예컨대, 스핀-온 또는 CVD 공정에 의해 제조된 비정질 탄소)의 치수 저하가, 예를 들어 약 100℃의 온도에서 수행되는 열적 ALD 동안 효과적으로 억제(예컨대, 하부층의 수축 감소)될 수 있고, 또는 하부층으로서 실리콘 기판의 산화가, 예를 들어 약 300℃의 온도에서 수행되는 열적 ALD 동안 효과적으로 억제(예컨대, 하부층의 산화된 부분의 두께 감소)될 수 있다. 제1 산화막이 열적 ALD에 의해 증착된 후, PEALD에 의해 제2 산화막이 제1 산화막 상에 연속적으로 증착된다. 하부층은 PEALD에서 사용되는 플라즈마로부터 제1 산화막에 의해 보호되기 때문에, 하부층은 PEALD에 의해 손상되지 않는다.
일부 구현예에서, 산화막은 패터닝된 리세스, 예컨대 트렌치를 갖는 기판 상에 효과적으로 증착된다. 본 개시에서, 인접하는 수직 스페이스들 사이의 리세스 및 임의의 다른 리세스 패턴은 "트렌치"로 지칭된다. 즉, 트렌치는 수직 스페이서로 형성된 패턴을 포함하는 임의의 리세스 패턴이고, 일부 구현예에서, 약 20 nm 내지 약 100 nm의 폭(전형적으로 약 30 nm 내지 약 50 nm)(여기서, 트렌치의 길이가 실질적으로 폭과 동일할 때, 이는 홀/비아(via)로 지칭되며, 이들의 직경은 약 20 nm 내지 약 100 nm임), 약 30 nm 내지 약 100 nm의 깊이(전형적으로 약 40 nm 내지 약 60 nm), 그리고 약 1 내지 약 10의 종횡비(전형적으로 약 2 내지 약 5)를 갖는다. 트렌치의 적절한 치수는 공정 조건, 막 조성물, 의도된 용도 등에 따라 달라질 수 있다.
열적 ALD에 의한 제1 산화막의 막 품질은 PEALD에 의한 제2 산화막의 막 품질만큼 좋지 않아서, 동일한 반응 챔버에서 열적 ALD와 PEALD를 연속적으로 수행함으로써, 제1 산화막의 표면을 보호하기 위해 제1 산화막이 분위기(예컨대, 공기)에 노출되는 것을 피한다. 일반적으로, 제1 산화막은 제2 산화막보다 높은 습식 식각율과 낮은 밀도를 가진다. 제1 산화막과 제2 산화막은 연속적으로 증착되기 때문에, 제1 및 제2 산화막에 의해 구성되는 막은 ALD에 의한 단일 산화막인 것으로 간주되고, 여기서 제1 산화막은 보호막으로서 작용하고, 반면에 제2 산화막은 결합된 산화막의 전체 특성을 결정하거나 조절하는 벌크층으로서 기능한다. 일부 구현예에서, 제1 산화막은 약 1 nm 내지 약 7 nm(예컨대, 약 2 nm 내지 약 5 nm)의 두께를 가지고, 제2 산화막은 약 5 nm 내지 약 30 nm(예컨대, 약 8 nm 내지 20 nm)의 두께를 가지며, 제2 산화막은 제1 산화막보다 두껍다.
열적 ALD에 의한 제1 산화막과 PEALD에 의한 제2 산화막이 연속적으로 증착되지만, 경계 또는 계면에서 Si, O, H, C 등의 농도 변화를 나타내는, 예를 들어 SIMS(Secondary ion mass spectroscopy)에 의한 조성 분석에 의해 이들 사이의 경계 또는 계면은 드러나거나 구분될 수 있다. 예를 들어, 열적 ALD에 의한 제1 산화막과 PEALD에 의한 제2 산화막 모두 동일 온도(예컨대, 100℃)에서 증착될 때, PEALD에서보다 열적 ALD에서의 반응성이 약하기 때문에, 동일한 전구체를 사용할 때 조차도 제1 산화막은 제2 산화막보다 높은 탄소 및 수분 농도를 가진다. STEP(Scanning Transmission Electron Microscopy)에 의한 구조 관찰은 경계 또는 계면을 드러나게 할 수 있지 않을 수 있다.
일부 구현예에서, 열적 ALD의 한 사이클은 전구체를 반응 챔버에 공급하는 단계를 포함하고, 상기 전구체는 아미노실란, 실릴아민, 이소시아네이트실란, 이소토네이트실란、무기 실란, 실란 함유 수산화물, 및 실란 함유 알콕사이드로 구성되는 군으로부터 선택되는 적어도 하나의 화합물의 가스이다. 일부 구현예에서, 전구체는 실리콘 대신, 예를 들어 TiO, ZrO 및 HfO로 구성되는 막을 형성하는 Ti, Zr 및 Hf과 같은 금속을 함유한다.
일부 구현예에서, 열적 ALD의 한 사이클은 반응물을 반응 챔버에 공급하는 단계를 포함하고, 상기 반응물은 H2O, 에테르, 알콜(예컨대, 메탄올, 에탄올 등), H2 및 O2의 혼합물, 및 H2O2로 구성되는 군으로부터 선택되는 적어도 하나의 가스이다. 기판의 표면 상에 흡착된 전구체와 반응하기 위해 이 반응물은 플라즈마 없이 여기될 수 있다. 이처럼, 반응물의 반응성에 따라 반응물을 반응 챔버에 공급하는 일반적으로 세 가지 방법(즉, 반응 챔버 내부에 제공된 샤워헤드의 매니폴드 도관 상류에 반응물을 유입시킴으로써, 반응물을 샤워헤드에서 유입시킴으로써, 및/또는 반응물을 기판이 배치되는 서셉터와 샤워헤드 사이에 유입시킴으로써 반응물을 반응 챔버에 공급하는 방법)이 있지만, 적절한 공급 방법이 선택되어야만 한다.
일부 구현예에서, PEALD의 한 사이클은 연속적으로 흐르는 캐리어 가스를 이용한 펄스로 전구체를 반응 챔버에 공급하는 단계, 및 반응물을 반응 챔버에 연속적으로 공급하는 단계를 포함한다. 일부 구현예에서, 반응물은 O2, CO2, 및 N2O로 구성되는 군으로부터 선택되는 적어도 하나의 가스이다.
일부 구현예에서, 열적 ALD의 한 사이클은 그 사이클을 통하여 연속적으로 반응물을 반응 챔버에 공급하는 단계를 포함하고, 이 반응물은 에탄올, H2O, 및 O3로 구성되는 군으로부터 선택되는 적어도 하나의 가스이다. 반응물의 반응성이 높지 않을 때, 반응물은 반응 챔버를 통해 연속적으로 흐를 수 있다. 그러나, 반응성이 낮기 때문에, 원하는 두께를 갖는 막의 증착을 완료하는 데 긴 시간이 걸린다. 따라서, 일부 구현예에서, 열적 ALD의 한 사이클은 촉매 가스를 펄스로 반응 챔버에 공급하는 단계를 포함하고, 이 촉매 가스는 전구체 및 반응물 이외의 가스이고 그 사이클에서 산화막의 증착을 촉진시킬 수 있다. 촉매 가스를 공급함으로써, 열적 ALD에 대한 막 증착율은 상당히 개선될 수 있고, 반응성이 낮을 수 있는 반응물 가스를 연속적으로 흐를 수 있게 한다. PEALD에서뿐만 아니라 ALD에서 반응물이 연속적으로 흐르면, 열적 ALD 및 PEALD를 위해 상이한 반응물들이 요구될 수 있지만, 반응 챔버 내의 압력은 열적 ALD의 사이클 및 PEALD의 사이클에 걸쳐서 실질적으로 일정하게 된다.
일부 구현예에서, 촉매 가스는 피리딘, 알킬 금속, 피리딜실란, 실릴아민, 및 실라잔(silazane)으로 구성되는 군으로부터 선택되는 적어도 하나의 화합물의 가스이다.
일부 구현예에서, 증착 방법은 열적 ALD 및 PEALD에 의한 증착을 수행한 후 반응 챔버를 세정하는 단계를 더 포함한다. 열적 ALD 및 PEALD 후에 동일한 세정 공정이 수행될 수 있다. 일부 구현예에서, 가스 혼합 챔버, 샤워헤드의 통로, 반응 챔버, 배기 통로 등이 세정될 수 있도록, 전구체와 반응물이 가스 혼합 챔버에서 혼합되는 위치의 상류로 세정 가스를 공급함으로써 세정 가스를 이용한 세정이 수행된다. 일부 구현예에서 세정 가스는 반응 챔버 상류에서 리모트 플라즈마 유닛에 의해 여기되거나 불소 함유 가스(예컨대, ClF3)를 사용하여 인-시튜로 여기된다. 일부 구현예에서, 세정은 열적 ALD의 한 사이클 및 PEALD의 한 사이클로 구성되는 n번의 반복 증착 사이클의 매회 후에 수행되고, n번의 반복은 반응 챔버의 내벽 상에 증착된 원치않는 막 등이 내벽으로부터 벗겨지기 시작하여 오염물 입자들을 생성시키는 반복 횟수보다 작다.
구현예가 도면을 기준으로 설명될 것이다. 그러나, 본 발명은 이러한 도면에 한정되지 않는다.
도 2는, 본 발명의 구현예에 따른 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다. 도 2에 도시된 시퀀스에서, 전구체는 연속적으로 공급되는 캐리어 가스 및 희석 가스(집합적으로는 "불활성 가스"로 지칭)를 사용하여 펄스("피드(Feed))로 공급된다. 이는, 캐리어 가스 라인이 전구체 리저버(용기)를 갖는 우회 라인(detour line)을 구비하고 메인 라인과 우회 라인이 스위칭되는, 유동-통과 시스템(FPS)을 이용하여 달성될 수 있고, 캐리어 가스만을 반응 챔버에 투입하고자 할 때에는 우회 라인이 닫히고, 반면 캐리어 가스와 전구체 가스 모두를 반응 챔버에 투입하고자 할 때에는 메인 라인이 닫히게 되어, 캐리어 가스는 우회 라인을 통해 흐르고 전구체 가스와 함께 용기로부터 흘러 나온다. 이러한 방식으로, 캐리어 가스는 반응 챔버 내로 연속해서 흐를 수 있고, 메인 라인과 우회 라인을 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 나타난 바와 같이, 전구체를 반응 챔버(미도시)에 투입할 때, 우선, Ar(또는 He)과 같은 캐리어 가스가 밸브 b 및 c를 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 e를 갖는 가스 라인을 통해 흐른 다음 전구체와 함께 반응 챔버에 공급된다. 위에서, 밸브 a 및 d는 닫힌다. 캐리어 가스(비활성 가스)만을 반응 챔버에 공급할 때, 도 1b의 (b)에 나타난 바와 같이, 캐리어 가스는 용기(20)를 우회하면서 밸브를 갖는 가스 라인을 통해 흐른다. 위에서, 밸브 b, c, d, e, 및 f는 닫힌다.
도 2에서, 전구체는 캐리어 가스의 도움으로 제공된다. ALD는 자기-제한 흡착 반응 공정이므로, 증착된 전구체 분자들의 개수는 반응성 표면 사이트의 개수에 의해 결정되며 포화 후 전구체의 노출과는 무관하고, 전구체의 공급은 사이클마다 반응성 표면 사이트가 포화되도록 한다. 증착 반응을 위한 반응물은 펄스("리액트(React)")로 반응 챔버에 공급되는 데, 이 때 반응물은 기판 상에 흡착된 전구체의 표면 상에 노출된 사이트(예컨대, -CH3)와 반응하기 위해 열적으로 활성화(예컨대, 증기 H2O)되고, 반면에 불활성 가스는 전구체의 공급 없이 연속적으로 반응 챔버에 공급되어 단층을 형성한다.
위에서 언급한 바와 같이, 각각의 증착 사이클의 각각의 펄스 또는 상(Phase)은 바람직하게 자기-제한적이다. 과량의 전구체가 각각의 상(phase)에 공급되어 민감한 구조 표면을 포화시킨다. 표면 포화는 이용가능한 모든 반응 사이트(예컨대, 물리적 크기 또는 "입체 장애" 제한에 대한 대상)의 전구체 점유를 보장하므로 우수한 단차 피복성을 보장한다. 일부 구현예에서, 완전한 포화를 달성하지 않고, 단층 미만으로 기판 표면에 흡착되도록, 하나 이상의 전구체의 펄스 시간이 감소될 수 있다. "피드" 후, 반응 챔버는 퍼지되고("퍼지 1"), 여기서 어떠한 전구체도 반응 공간에 공급되지 않으며, 반면 불활성 가스는 반응물의 공급 없이 반응 챔버에 연속적으로 공급되어, 화학 흡착되지 않은 전구체 및 과잉 가스를 기판의 표면으로부터 제거한다. "리액트" 후, 반응 공간은 퍼지되고("퍼지 2"), 여기서 반응 챔버에 전구체와 반응물을 공급하지 않고서 불활성 가스가 반응 챔버에 연속적으로 공급되어, 부산물 및 과잉 가스를 기판의 표면으로부터 제거한다. 전구체가 간헐적으로 또는 펄스로 주입되는 일정한 스트림으로서 반응 챔버에 진입하는 불활성 가스의 연속적인 흐름으로 의해, 퍼징이 효율적으로 수행되어 과잉 가스 및 부산물을 층의 표면으로부터 신속하게 제거할 수 있어서, 원하는 두께의 층이 얻어질 때까지 다중 열적 ALD 사이클들을 효율적으로 계속할 수 있다.
도 4는, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다. 도 4에 도시된 시퀀스에서, 전구체는 연속적으로 공급되는 캐리어 가스 및 희석 가스(집합적으로는 "불활성 가스"로 지칭)를 사용하여 펄스("피드(Feed))로 공급된다. 이는 도 2의 공정 시퀀스와 관련하여 전술한 바와 같이 유동-통과 시스템(FPS)을 사용하여 이루어질 수 있다.
도 4에서, 전구체는 캐리어 가스("불활성 가스")의 도움으로 제공된다. ALD는 자기-제한 흡착 반응 공정이므로, 증착된 전구체 분자들의 개수는 반응성 표면 사이트의 개수에 의해 결정되며 포화 후 전구체의 노출과는 무관하고, 전구체의 공급은 사이클마다 반응성 표면 사이트가 포화되도록 한다. 증착 사이클에 걸쳐 연속적으로 흐르는 반응물 가스("반응물")(예컨대, O2)에 RF 전력을 인 시튜로 펄스("RF")로 인가함으로써 증착을 위한 플라즈마가 생성되고, 반면 불활성 가스 및 반응물은 전구체의 공급 없이 반응 챔버에 연속적으로 공급되어 단층을 형성한다.
도 2의 시퀀스와 관련하여 전술한 바와 같이, 과량의 전구체가 공급되어 민감한 구조물 표면을 포화시킨다. 일부 구현예에서, 완전한 포화를 달성하지 않고, 단층 미만으로 기판 표면에 흡착되도록, 하나 이상의 전구체의 펄스 시간이 감소될 수 있다. "피드" 후, 반응 공간은 퍼지되고("퍼지 1"), 여기서 전구체는 반응 공간에 투입되지 않으며, 반면 불활성 가스 및 반응물 가스는 RF 전력의 인가 없이 반응 공간에 연속적으로 공급되어, 화학 흡착되지 않은 전구체 및 과잉 가스를 기판의 표면으로부터 제거한다. "RF" 후, 반응 공간은 퍼지되고("퍼지 2"), 여기서 반응 공간에 전구체를 공급하지 않고 RF 전력을 인가하지 않고서, 불활성 가스 및 반응물 가스가 반응 공간에 연속적으로 공급되어, 부산물 및 과잉 가스를 기판의 표면으로부터 제거한다. 반응물 가스의 연속적인 흐름으로 인해 그리고 또한 전구체가 간헐적으로 또는 펄스로 주입되는 일정한 스트림으로서 반응 공간에 진입하는 불활성 가스의 연속적인 흐름으로 의해, 퍼징이 효율적으로 수행되어 과잉 가스 및 부산물을 층의 표면으로부터 신속하게 제거할 수 있어서, 원하는 두께의 층이 얻어질 때까지 다중 PEALD 사이클들을 효율적으로 계속할 수 있다.
도 3은, 본 발명의 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스와 조합된 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다. 하나의 사이클에 열적 ALD 및 PEALD가 결합된 이러한 연속 공정 시퀀스에서, 열적 ALD는 "피드 1", "퍼지 1", "리액트 1" 및 "퍼지 2"를 포함하고, 이들은 각각 도 2에 도시된 "피드", "퍼지 1", "리액트", 및 "퍼지 2"에 대응한다. 상기 사이클을 m번(m은 1 내지 3000, 바람직하게는 1 내지 500의 정수) 반복한 후, 도 4에 도시된 "피드", "퍼지 1", "RF", 및 "퍼지 2"에 각각 실질적으로 대응하는 "피드 2", "퍼지 3", "RF", 및 "퍼지 4"를 포함하는 PEALD가 시작된다. 상기한 사이클은 n번(n은 1 내지 1000, 바람직하게는 1 내지 150의 정수) 반복될 수 있다. n/m의 비는 0.1 내지 3, 바람직하게는 0.2 내지 1의 범위 내에 있을 수 있다.
열적 ALD에서, 반응물의 반응성은 일반적으로 낮으므로, 알콕시드 실란과 같이 높은 반응성을 가진 반응물이 사용되지 않으면, PEALD와 비교하여 증착율은 일반적으로 낮다. 낮은 반응성을 갖는 반응물이 사용될 때, 피리딘과 같은 촉매를 첨가함으로써 반응성은 상당히 개선될 수 있는 데, 여기서 단층의 표면 상에 노출된 예를 들어, SiO-H 결합은 촉매에 의해 약화되어 반응물 종의 반응성 및 흡착된 전구체의 노출된 사이트들을 증가시킨다. 도 5는, 본 발명의 구현예에 따른 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다. 도 5에 도시된 시퀀스에서, 전구체는 연속적으로 공급되는 캐리어 가스 및 희석 가스(집합적으로는 "불활성 가스"로 지칭)를 사용하여 펄스("피드 1")로 공급된다. 이는 도 2의 공정 시퀀스와 관련하여 전술한 바와 같이 유동-통과 시스템(FPS)을 사용하여 이루어질 수 있다.
도 5에서, 전구체는 캐리어 가스("불활성 가스")의 도움으로 제공된다. ALD는 자기-제한 흡착 반응 공정이므로, 증착된 전구체 분자들의 개수는 반응성 표면 사이트의 개수에 의해 결정되며 포화 후 전구체의 노출과는 무관하고, 전구체의 공급은 사이클마다 반응성 표면 사이트가 포화되도록 한다. 반응물 및 전구체의 반응성을 높이기 위한 촉매는 증착 사이클에 걸쳐 연속적으로 흐르는 펄스("피드 2")로 반응 챔버에 공급되고, 반면 반응물 및 불활성 가스는 전구체의 공급 없이 반응 챔버에 연속적으로 공급되어 단층을 형성한다. 반응물의 반응성이 낮기 때문에, 반응물은 사이클에 걸쳐 연속적으로 흐를 수 있고, 촉매를 펄스로 공급함으로써, 증착 반응은 활성화될 수 있다. 열적 ALD를 위한 연속 반응물 유동은 알려져 있지 않고, 압력 변동은 최소화되거나 실질적으로 억제될 수 있고, 조절능은 증가된다.
도 2의 시퀀스와 관련하여 전술한 바와 같이, 과량의 전구체가 각 상에서 공급되어 민감한 구조물 표면을 포화시킨다. 일부 구현예에서, 완전한 포화를 달성하지 않고, 단층 미만으로 기판 표면에 흡착되도록, 하나 이상의 전구체의 펄스 시간이 감소될 수 있다. "피드 1" 후, 반응 챔버는 퍼지되고("퍼지 1"), 여기서 어떠한 전구체도 반응 공간에 공급되지 않으며, 반면 불활성 가스 및 반응물 가스는 촉매의 공급 없이 반응 공간에 연속적으로 공급되어, 화학 흡착되지 않은 전구체 및 과잉 가스를 기판의 표면으로부터 제거한다. "피드 2" 후, 반응 챔버는 퍼지되고("퍼지 2"), 여기서 반응 챔버에 전구체와 촉매를 공급하지 않고서 불활성 가스 및 반응물 가스가 반응 공간에 연속적으로 공급되어, 부산물 및 과잉 가스를 기판의 표면으로부터 제거한다. 반응물 가스의 연속적인 흐름으로 인해 그리고 또한 전구체 및 촉매가 각각 간헐적으로 또는 펄스로 주입되는 일정한 스트림으로서 반응 공간에 진입하는 불활성 가스의 연속적인 흐름으로 의해, 퍼징이 효율적으로 수행되어 과잉 가스 및 부산물을 층의 표면으로부터 신속하게 제거할 수 있어서, 원하는 두께의 층이 얻어질 때까지 다중 열적 ALD 사이클들을 효율적으로 계속할 수 있다.
도 6은, 본 발명의 다른 구현예에 따른 한 사이클에서 PEALD의 개략적인 공정 시퀀스와 조합된 한 사이클에서 열적 ALD의 개략적인 공정 시퀀스를 나타내며, 회색의 셀은 온 상태를 표시하고, 반면 흰색의 셀은 오프 상태를 표시하나, 각 컬럼의 폭이 각 공정의 지속시간을 표시하는 것은 아니다. 하나의 사이클에 열적 ALD 및 PEALD가 결합된 이러한 연속 공정 시퀀스에서, 열적 ALD는 "피드 1", "퍼지 1", "피드 2" 및 "퍼지 2"를 포함하고, 이들은 각각 도 5에 도시된 것들에 대응한다. 상기 사이클을 m번(m은 1 내지 3000, 바람직하게는 1 내지 1000의 정수) 반복한 후, 도 4에 도시된 "피드", "퍼지 1", "RF", 및 "퍼지 2"에 각각 실질적으로 대응하는 "피드 3", "퍼지 3", "RF", 및 "퍼지 4"를 포함하는 PEALD가 시작된다. 상기한 사이클은 n번(n은 1 내지 1000, 바람직하게는 1 내지 150의 정수) 반복될 수 있다. n/m의 비는 0.1 내지 3, 바람직하게는 0.2 내지 2의 범위 내에 있을 수 있다. 이러한 시퀀스에서, 압력 변동은 최소화 되거나 실질적으로 억제될 수 있고, 조절능은 증가된다.
공정 사이클은, 예를 들면 도 1a에 도시된 장치를 포함하는 임의의 적합한 장치를 사용하여 수행될 수 있다. 도 1a는 본 발명의 일부 구현예에서 사용할 수 있는 산화막을 증착하기 위한, 바람직하게는 아래에 기술된 시퀀스들을 수행하도록 프로그램된 조절들과 관련하여, 산화막을 증착하는 열적 ALD 및 플라즈마 강화 ALD(PEALD)를 위한 원자층 증착(ALD) 장치의 개략적인 표시이다. 이 도면에서, 서로 마주하며 평행한 한 쌍의 전기 전도성(용량 결합성) 평판 전극(4, 2)을 반응 챔버(3)의 내부(반응 구역)(11)에 제공하고, 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 제공되고, 그 위에 놓인 기판(1)의 온도는 주어진 온도로 일정하게 유지된다. 상부 전극(4)은 샤워 플레이트(shower plate)로서의 역할도 수행하며, 전구체 가스 및 반응물 가스 (및 비활성 가스)는 각각의 가스 라인(21) 및 가스 라인(22)을 통해서 그리고 PEALD용 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 표면 처리는 동일한 반응 공간에서 수행되어, 모든 단계들이 기판을 공기 또는 다른 산소-함유 대기에 노출시키지 않고 연속적으로 수행될 수 있다.
일부 구현예에서, 제1 산화막 및 제2 산화막이 하나의 (단일막 형태의) 연속 산화막을 구성하더라도, 열적 ALD에 의한 제1 산화막의 경우, PEALD에 의한 제2 산화막을 위해 사용된 것들과는 상이한 전구체 및 반응물이 사용된다. 열적 ALD에서, 전구체 및 반응물은 접촉시 서로 반응하려는 경향이 있으므로, 일부 구현예에서, 반응물은 PEALD를 위한 반응물을 공급하기 위한 포트와 상이한 포트를 사용하여 반응 챔버에 공급된다. 도 1a에 도시된 장치에서, 열적 ALD를 위한 반응물은, 반응 챔버(3) 내에 제공되는 샤워헤드(4)의 상류 가스 라인(27)을 통해 매니폴드 도관(23)에 반응물을 유입시키고/유입시키거나 샤워헤드(4)에 제공되는 가스 포트(18)를 통해 샤워헤드(4)에 반응물을 유입시키고/유입시키거나 기판(1)이 놓이는 서셉터(2)와 샤워헤드(4) 사이에 반응 챔버(3)의 측벽에 제공되는 가스 포트(17)(원형 덕트(13)를 통하여 기밀 침투)를 통하여 반응물을 유입시킴으로써 반응 챔버에 공급될 수 있다. 열적 ALD의 경우, 상이한 전구체가 사용되면, 전구체는 가스 라인(26)을 통해 매니폴드 도관(23)에 공급된다. 일부 구현예에서, 여기된 가스를 매니폴드 도관(23)에 공급함으로써 가스를 여기시키기 위해 리모트 플라즈마 유닛이 사용될 수 있다.
일부 구현예에서, 도 1a에 묘사된 장치에서, 도 1b에 도시된(앞에서 설명된) 불활성 기체의 흐름 및 전구체 가스의 흐름을 스위칭하는 시스템이, 반응 챔버의 압력을 변동시키지 않고 전구체 가스를 펄스로 유입하기 위해 사용될 수 있다.
일부 구현예에서, 듀얼 챔버 반응기(서로 근접하게 배치된 웨이퍼를 프로세싱하기 위한 두 개의 섹션 또는 컴파트먼트)가 사용될 수 있고, 반응물 가스 및 비활성 가스는 공유된 라인을 통해 공급될 수 있고, 반면 전구체 가스는 공유되지 않는 라인을 통해 공급된다.
당업자는 프로그램된, 그렇지 않으면 증착 및 본원의 다른 곳에서 설명되는 반응기 세정 공정이 수행되도록 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 밸브들과 통신한다.
도 7은 본 발명의 다른 구현예에 사용할 수 있는 산화막을 증착하는 열적 ALD 및 플라즈마 강화 ALD(PEALD)를 위한 장치의 개략적인 표시이다. 이 장치에서, 가스 라인(31, 32, 33 및 34)은 도 1a에 도시된 장치의 가스 라인(21, 22, 26 및 27)에 대응하고; RF 소스(51)는 도 1a의 RF 소스(25)에 대응하고; 매니폴드 도관(41)은 도 1a의 매니폴드 도관(23)에 대응하고; 샤워헤드(44)는 도 1a의 샤워헤드(4)에 대응하고; 반응 챔버(52)는 도 1a의 반응 챔버(3)에 대응하고; 배기 라인(45)은 도 1a의 배기 라인(6)에 대응하고; 서셉터(43)는 도 1a의 서셉터(2)에 대응한다. 도 1a에 나타나 있는 임의 구조물들은 도 7에 도시된 장치에 제공될 수 있다. 게이트 밸브(42)는 리모트 플라즈마 유닛을 위한 게이트 밸브이다. 이 장치에서, 촉매는 반응 챔버(52)에 공급될 수 있다. 촉매는 전구체와 반응성이기 때문에, 일부 구현예에서, 촉매는 샤워헤드(44) 상류에서 전구체와 혼합되지 않고서 직접 반응 챔버(52)에 공급된다. 예를 들어, 도 1a에 도시된 바와 같이 전구체용 구멍들을 갖는 가스 통로와 분리된, 도 7에 도시된 바와 같이 샤워헤드(44)에 다른 구멍들(37)을 갖는 다른 가스 통로를 제공함으로써, 촉매는 가스 라인(35)을 통해 샤워헤드(44)에 구멍들(37)을 갖는 가스 통로로 공급될 수 있고, 그 결과 촉매가 반응 챔버(52)의 내부로 들어갈 때까지 촉매는 전구체와 접촉하지 않고서 반응 챔버에 공급될 수 있다(비록 도 7은 샤워헤드의 외주 근처에 분포된 구멍들(37)을 갖는 통로를 나타내고 있지만, 이 구멍들(37)은 샤워헤드의 전체 표면에 걸쳐 고르게 분포될 수 있다). 대안적으로 또는 추가적으로, 촉매는 반응 챔버(52)의 측벽에 제공되는 가스 포트(36)를 통하여 반응 챔버(52)에 공급될 수 있다.
일부 구현예에서, 열적 ALD 사이클들 및 PEALD 사이클들은 하기 표 1에 나타낸 조건들 하에서 도 3에 도시된 바와 같이 연속적으로 수행될 수 있다.
열적 ALD에 의한 제1 산화막을 위한 조건 | |
기판 온도 | 0 내지 500℃(패터닝의 경우 바람직하게는 50 내지 300℃°C; 층간 절연막의 경우, 예컨대 25 to 100°C) |
전극 갭(기판의 두께는 약 0.7 mm임) | 2 내지 15 mm(바람직하게는 5 내지 15 mm) |
압력 | 133 내지 3000 Pa(바람직하게는 200 내지 2000 Pa) |
제1반응물의 유량(펄스로) | 10 내지 10000 sccm(바람직하게는 50 내지 2000 sccm) |
캐리어 가스의 유량(연속적) | 500 내지 4000 sccm(바람직하게는 1000 내지 2000 sccm) |
희석 가스의 유량(연속적) | 0.1 내지 5 slm(바람직하게는 0.1 내지 2 slm) |
제1 전구체의 유량 | 캐리어 가스의 유량에 대응함 |
"피드 1"의 지속시간 | 0.1 내지 5초 (바람직하게는 0.1 내지 2초) |
"퍼지 1"의 지속시간 | 0.1 내지 5초 (바람직하게는 0.2 내지 1초) |
"리액트"의 지속시간 | 1 내지 600초 (바람직하게는 10 내지 240초) |
"퍼지 2"의 지속시간 | 1 내지 30초 (바람직하게는 1 내지 15초) |
한 사이클의 지속시간 | 2.2 내지 640초 (바람직하게는 4 내지 100초) |
사이클당 성장 속도(nm/min) | 상면에서 0.1 내지 1(바람직하게는 0.2 내지 0.5) |
사이클의 수(m번) | 1 내지 3000(바람직하게는 1 내지 1000) |
PEALD에 의한 제2 산화막을 위한 조건 | |
기판 온도 | 0 내지 500°C (패터닝의 경우 바람직하게는 50 내지 300°C; 층간 절연의 경우, 예컨대 25 to 100°C) |
전극 갭(기판의 두께는 약 0.7 mm임) | 2 내지 15 mm(바람직하게는 5 내지 15 mm) |
압력 | 133 내지 3000 Pa(바람직하게는 200 내지 2000 Pa) |
제2 반응물의 유량(연속적) | 10 내지 5000 sccm(바람직하게는 50 내지 2000 sccm) |
캐리어 가스의 유량(연속적) | 500 내지 5000 sccm(바람직하게는 1000 내지 2000 sccm) 또는 열적 ALD에서와 동일 |
희석 가스의 유량(연속적) | 0.1 내지 5 slm(바람직하게는 0.2 내지 2 slm) 또는 열적 ALD에서와 동일 |
제2 전구체의 유량 | 캐리어 가스의 유량에 대응함 |
300-mm 웨이퍼를 위한 RF 전력(13.56 MHz) | 50 내지 2000 W(바람직하게는 50 내지 200 W) |
"피드 2"의 지속시간 | 0.1 내지 2초 (바람직하게는 0.1 내지 1초) |
"퍼지 3"의 지속시간 | 0.1 내지 2초 (바람직하게는 0.2 내지 1초) |
"RF"의 지속시간 | 0.1 내지 5초 (바람직하게는 0.2 내지 2초) |
"퍼지 4"의 지속시간 | 0.1 내지 2초 (바람직하게는 0.1 내지 1초) |
한 사이클의 지속시간 | 0.4 내지 11초 (바람직하게는 0.6 내지 6초) |
사이클당 성장 속도(nm/min) | 상면에서 0.4 내지 15(바람직하게는 1 내지 10) |
사이클의 수(n번) | 10 내지 1000(바람직하게는 50 내지 350) |
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.
일반적으로, 제1 산화막의 두께는 약 1 nm 내지 약 7 nm 범위이고, 반면에 제2 산화막의 두께는 약 5 nm 내지 약 30 nm 범위이며, 제2 산화막의 두께는 제1 산화막의 두께보다 두껍다(원하는 막 두께는 막의 적용 및 목적 등에 따라 적절하다고 간주되는 두께로 선택될 수 있다). 결합된 산화막을 탄소막(예컨대, 비정질 탄소) 상에 증착함으로써 결합된 산화막은 이중 패터닝을 위해 사용될 수 있거나 결합된 산화막을 템플릿(예컨대, 실리콘 기판) 상에 증착함으로써 결합된 산화막은 층간 유전체막으로서 사용될 수 있다.
일부 구현예에서, 열적 ALD 사이클들 및 PEALD 사이클들은 하기 표 2에 나타낸 조건들 하에서 도 6에 도시된 바와 같이 연속적으로 수행될 수 있다.
열적 ALD에 의한 제1 산화막을 위한 조건 | |
기판 온도 | 25 내지 500°C (패터닝의 경우 바람직하게는 50 내지 300°C; 층간 절연의 경우, 예컨대 25 to 100°C) |
전극 갭(기판의 두께는 약 0.7 mm임) | 2 내지 15 mm(바람직하게는 5 내지 10 mm) |
압력 | 133 내지 3000 Pa(바람직하게는 200 내지 2000 Pa) |
제1반응물의 유량(펄스로) | 10 내지 10000 sccm(바람직하게는 50 내지 2000 sccm) |
캐리어 가스의 유량(연속적) | 500 내지 4000 sccm(바람직하게는 1000 내지 2000 sccm) |
희석 가스의 유량(연속적) | 0.1 내지 5 slm(바람직하게는 0.1 내지 2 slm) |
촉매의 유량(펄스로) | 0.5 내지 100 sccm(바람직하게는 1 내지 50 sccm, 예컨대 1~10 sccm) |
제1 전구체의 유량 | 캐리어 가스의 유량에 대응함 |
"피드 1"의 지속시간 | 0.1 내지 5초 (바람직하게는 0.1 내지 2초) |
"퍼지 1"의 지속시간 | 0.1 내지 5초 (바람직하게는 0.2 내지 1초) |
"피드 2"의 지속시간 | 1 내지 600초 (바람직하게는 10 내지 240초) |
"퍼지 2"의 지속시간 | 1 내지 30초 (바람직하게는 1 내지 15초) |
한 사이클의 지속시간 | 2.2 내지 640초 (바람직하게는 4 내지 100초) |
사이클당 성장 속도(nm/min) | 상면에서 0.1 내지 1(바람직하게는 0.2 내지 0.5) |
사이클의 수(m번) | 1 내지 3000(바람직하게는 1 내지 1000) |
PEALD에 의한 제2 산화막을 위한 조건 | |
표 1에서와 동일 |
제1 산화막 및 제2 산화막은 하기 표 3에 나타나 있는 성질들을 가질 수 있다.
제1 산화막 | 제2 산화막 | |
100:1 DHF; 상부 WER (nm/min) | 0.5 내지 20(바람직하게는 1 내지 10) | 0.2 내지 3(바람직하게는 0.2 내지 0.5) |
막 밀도(g/cm3) | 1.7 내지 2.4(바람직하게는 1.9 내지 2.2) | 2.0 내지 2.4(바람직하게는 2.1 내지 2.2) |
상기에서, 제1 산화막의 WER은 제2 산화막의 WER보다 낮고, 제1 산화막의 막 밀도는 또한 제2 산화막의 막 밀도보다 낮다.
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 내지 5
1의 단차비(100 nm의 개구부 폭)를 갖는 넓은 트렌치들 및 3.5의 단차비(30 nm의 개구부 폭)를 갖는 좁은 트렌치들을 갖는 실리콘 기판(300 mm의 직경 및 0.7 mm의 두께를 가짐) 상에 형성된 비정질 탄소막(100 nm의 두께를 가짐) 상에 도 3 또는 도 4에 도시된 시퀀스를 이용하는 열적 ALD 및 PEALD의 결합 공정에 의해 실리콘 산화막을 형성하였는 데, 이 결합 공정의 한 사이클은, 하기 표 4(공정 사이클)에 나타나 있는 공통 조건들 하에서 도 1a에 도시된 ALD 장치 및 특정 조건들 및 표 5에 나타낸 시퀀스를 갖는 도 1b에 도시된 가스 공급 시스템(FPS)을 사용하여 수행되었다. 도 1a에 도시된 매니폴드 도관을 통하여 제1 반응물을 반응 챔버에 공급하였다.
공정 사이클을 위한 공통 조건 | ||
캐리어 가스 및 희석 가스 | Ar | |
캐리어 가스의 유량(연속적) | 2 slm | |
압력 | 400 Pa | |
전극들 간 거리 | 12 mm | |
열 적 A L D |
증착된 막 종류 | SiO |
막의 전체 두께 | 표 5 참조 | |
제1 전구체 | 표 5 참조 | |
제1 반응물 | 표 5 | |
제1반응물의 유량(펄스로) | 50 sccm | |
제1 반응물 온도 조절 | 없음(상온) | |
도 3에서 "피드 1" | 0.3초 | |
도 3에서 "퍼지 1" | 0.3초 | |
도 3에서 "리액트" | 3초(공급 1초, 반응 2초) | |
도 3에서 "퍼지 2" | 0.1초 | |
P E A L D |
증착된 막 종류 | SiO |
막의 전체 두께 | 10 nm | |
제2 전구체 | BDEAS(b는 (디에틸아미노)실란) | |
제2 반응물 | O2 | |
제2 반응물의 유량(연속적) | 100 sccm | |
RF 전력(13.56 MHz) | 100 W | |
도 3에서 "피드 2" | 0.3초 | |
도 3에서 "퍼지 3" | 0.3초 | |
도 3에서 "RF" | 0.2초 | |
도 3에서 "퍼지 4" | 0.1초 |
공정 | 시퀀스 |
온도 () |
제1 전구체 | 제1 반응물 | 제1 산화막 두께 (mm) |
|
*1 | PEALD | 도 4 | 100 | - | - | - |
2 | 열적 + PEALD | 도 3 | 100 | BDEAS | 에탄올 | 2 |
3 | 열적 + PEALD | 도 3 | 100 | TICS(tetra isocyanato silane) | 에탄올 | 2 |
4 | 열적 + PEALD | 도 3 | 100 | BDEAS | H2O | 2 |
5 | 열적 + PEALD | 도 3 | 100 | TICS | H2O | 2 |
표 5에서, "*"가 있는 실시예 번호는 비교예(들)를 가리킨다. 얻어진 각각의 막을 평가하였다. 표 6은 평가 결과를 나타낸다.
탄소막 수축 (%) |
측벽 피복 (%) |
패턴 로딩 (%) |
열적 ALD GPC (nm/cycle) |
|
*1 | 3 | 95 | 95 | - |
2 | 0.6 | 95 | 95 | 0.001 |
3 | 0.3 | 97 | 96 | 0.002 |
4 | 0.6 | 95 | 95 | 0.001 |
5 | 0.3 | 94 | 94 | 0.002 |
표 6에서, "탄소막 수축"은 산화막의 증착 전 탄소막의 두께에 대한 산화막의 증착 후 감소된 탄소막의 두께의 비의 백분율을 표시하고; "측벽 피복율"은 기판의 상면에서 산화막의 두께에 대한 좁은 트렌치들의 측벽들에서 산화막의 두께의 비의 백분율을 표시하고; "패턴 로딩"은 넓은 트렌치들의 측벽들에서 산화막의 두께에 대한 좁은 트렌치들의 측벽들에서 산화막의 두께의 비의 백분율을 표시하고; "열적 ALD GPC"는 사이클당 성장율을 표시한다.
표 6에 도시된 바와 같이, 실리콘 산화막이 PEALD에 의해서만 증착되었으면, 하부 탄소막은 손상되었으며 상당한 막 수축을 나타내었고(실시예 1), 반면에 실리콘 산화막이 보호층으로서 열적 ALD에 의해 먼저 증착되었고, 이후 벌크층으로서 PEALD에 의해 연속적으로 증착되었으면, 하부 탄소막은 훨씬 덜 손상되었고 상당히 더 낮은 막 수축을 나타내었다(실시예 2~5). 또한, 보호층으로서, TICS를 이용한 열적 ALD에 의한 실리콘 산화막(실시예 3과 5)은 BDEAS를 사용한 산화막(실시예 2와 4)보다 더 좋은 것으로 나타났다. 추가적으로, PEALD 공정에 의해 증착된 실리콘 산화막(실시예 1)의 등각성 및 열적 ALD와 PEALD의 결합 공정에 의해 증착된 실리콘 산화막(실시예 2~5)의 등각성은 상당히 상이하지 않았다(이들 모두는 90%의 등각성을 초과했다).
실시예 6 내지 11
표 7에 나타낸 특정 조건 및 시퀀스를 갖는 탄소막 없이 산화막이 실리콘 기판 상에 직접 증착되었던 것을 제외하고는 실시예 1 내지 5에 기술된 방식과 실질적으로 동일한 방식으로 실리콘 산화막을 실리콘 기판 상에 형성하였다.
공정 | 시퀀스 |
온도 () |
제1 전구체 | 제1 반응물 | 제1 산화막 두께 (mm) |
|
*6 | PEALD | 도 4 | 400 | - | - | - |
7 | 열적 + PEALD | 도 3 | 300 | BDEAS | 에탄올 | 2 |
8 | 열적 + PEALD | 도 3 | 300 | TICS | 에탄올 | 2 |
9 | 열적 + PEALD | 도 3 | 300 | TICS | 에탄올 | 5 |
10 | 열적 + PEALD | 도 3 | 300 | OMCTS(octamethylcyclotetrasiloxane) | 에탄올 | 5 |
11 | 열적 + PEALD | 도 3 | 300 | OMCTS | H2O | 5 |
표 7에서, "*"가 있는 실시예 번호는 비교예(들)를 가리킨다. 얻어진 각각의 막을 평가하였다. 표 8은 평가 결과를 나타낸다.
산화된 Si 기판의 두께 (nm) | 측벽 피복율 (%) |
패턴 로딩 (%) |
열적 ALD GPC (nm/cycle) |
|
*6 | 1.5 | 95 | 95 | - |
7 | 0.2 | 96 | 93 | 0.0009 |
8 | 0.2 | 94 | 97 | 0.002 |
9 | 0 | 98 | 101 | 0.002 |
10 | 0.2 | 94 | 94 | 0.01 |
11 | 0.3 | 93 | 96 | 0.02 |
표 8에서, 산화된 Si 기판의 두께"는 산화막의 증착 후 관찰을 기준으로 산화된 실리콘 기판의 두께를 표시한다.
표 8에 도시된 바와 같이, 실리콘 산화막이 PEALD에 의해서만 증착되었으면, 하부 실리콘층은 손상되었고 산화되었으며(실시예 6), 반면에 실리콘 산화막이 보호층으로서 열적 ALD에 의해 먼저 증착되었고, 이후 벌크층으로서 PEALD에 의해 연속적으로 증착되었으면, 하부 실리콘층은 훨씬 덜 손상되었고 산화되었다(실시예 7~11). 또한, 보호층으로서, TICS를 이용한 열적 ALD에 의한 실리콘 산화막(실시예 9)은 OMCTS를 이용한 산화막(실시예 10과 11)보다 더 나은 것으로 나타났고, 또한 5 nm의 두께를 갖는 실리콘 산화막(실시예 9)은 2 nm의 실리콘 산화막(실시예 8)보다 더 나았다. OMCTS를 이용한 열적 ALD에 의해 증착된 실리콘 산화막(실시예 10과 11)은 TICS를 이용한 열적 ALD에 의해 증착된 실리콘 산화막(실시예 9)보다 상당히 높은 GPC를 나타내었다(알콕시드 실란이 높은 반응성을 갖기 때문). 추가적으로, PEALD 공정에 의해 증착된 실리콘 산화막(실시예 6)의 등각성 및 열적 ALD와 PEALD의 결합 공정에 의해 증착된 실리콘 산화막(실시예 7~11)의 등각성은 상당히 상이하지 않았다(이들 모두는 90%를 초과했다).
실시예 12 내지 17
제1 반응물이 연속적으로 공급되었다는 점과 도 2, 4, 5 또는 6에 도시된 시퀀스를 사용하여 촉매가 첨가되었다는 점을 제외하면, 실시예 1 내지 5와 실질적으로 동일한 방식으로 비정질 탄소막 상에 실리콘 산화막을 형성하였고, 이 ? 한 사이클은 하기 표 9(공정 사이클)에 나타나 있는 공통 조건 하에서 표 10에 나타낸 특정 조건 및 시퀀스를 갖고서 수행되었다. 촉매는 도 7에 도시된 상이한 가스 경로를 경유하여 샤워헤드를 통해 반응 챔버에 공급되었다.
공정 사이클을 위한 공통 조건 | ||
캐리어 가스 및 희석 가스 | Ar | |
캐리어 가스의 유량(연속적) | 2 slm | |
압력 | 400 Pa | |
전극들 간 거리 | 12 mm | |
열 적 A L D |
증착된 막 종류 | SiO |
막의 전체 두께 | 표 10 참조 | |
제1 전구체 | BDEAS | |
제1 반응물 | 표 10 참조 | |
제1 반응물의 유량(연속적) | 50 sccm | |
제1 반응물 온도 조절 | 상온 | |
촉매 | 피리딘 | |
촉매의 유량(펄스로) | 3 sccm | |
도 6에서 "피드 1" | 0.3초 | |
도 6에서 "퍼지 1" | 0.3초 | |
도 6에서 "피드 2" | 5초 | |
도 6에서 "퍼지 2" | 0.1초 | |
P E A L D |
증착된 막 종류 | SiO |
막의 전체 두께 | 10 nm | |
제2 전구체 | BDEAS | |
제2 반응물 | O2 | |
제2 반응물의 유량(연속적) | 100 sccm | |
RF 전력(13.56 MHz) | 100 W | |
도 3에서 "피드 2" | 0.3초 | |
도 3에서 "퍼지 3" | 0.3초 | |
도 3에서 "RF" | 0.2초 | |
도 3에서 "퍼지 4" | 0.1초 |
공정 | 시퀀스 | 온도 () |
제1 반응물 | 제1 산화막 두께 (mm) |
|
*12 | PEALD | 도 4 | 100 | - | - |
*13 | 열적 ALD | 도 2 | 100 | H2O | 10 |
*14 | 열적 ALD | 도 5 | 100 | H2O | 10 |
15 | 열적 + PEALD | 도 6 | 100 | H2O | 3 |
16 | 열적 + PEALD | 도 6 | 100 | H2O | 1 |
17 | 열적 + PEALD | 도 6 | 100 | 에탄올 | 1 |
표 10에서, "*"가 있는 실시예 번호는 비교예(들)를 가리킨다. 얻어진 각각의 막을 평가하였다. 표 11은 평가 결과를 나타낸다.
탄소막 수축 (%) |
측벽 피복율 (%) |
패턴 로딩 (%) |
열적 ALD GPC (nm/cycle) |
|
*12 | 3 | 95 | 95 | - (0.15) |
*13 | 0.5 | 94 | 94 | 0.001 |
*14 | 0.5 | 93 | 96 | 0.03 |
15 | ~0 | 97 | 99 | 0.04 |
16 | 0.5 | 98 | 95 | 0.05 |
17 | 0.4 | 91 | 92 | 0.04 |
표 11에서, 용어들은 표 6에서 사용된 용어들에 대응한다. "열적 ALD GPC"에서, 괄호 안의 숫자는 PEALD에 의한 GPC를 나타낸다.
표 11에 도시된 바와 같이, 실리콘 산화막이 PEALD에 의해서만 증착되었으면, 하부 탄소막은 손상되었으며 상당한 막 수축을 나타내었고(실시예 12), 반면에 실리콘 산화막이 보호층으로서 열적 ALD에 의해 먼저 증착되었고, 이후 벌크층으로서 PEALD에 의해 연속적으로 증착되었고(실시예 15~17), 실리콘 산화막이 열적 ALD에 의해서만 증착되었으면(실시예 13과 14), 하부 탄소막은 훨씬 덜 손상되었고 상당히 더 낮은 막 수축을 나타내었다. 또한, 놀랍게도, 제2 실리콘 산화막을 PEALD로 증착했을 때, 제2 실리콘 산화막을 증착하기 전에 제1 실리콘 산화막을 보호층으로서 1 nm 내지 3 nm의 두께로 열적 ALD로 증착함으로써(실시예 15~17), 하부막에 대한 플라즈마의 역효과를 완전히 피하였다(실시예 15~17에서 탄소막 수축은 열적 ALD만 수행되었던 실시예 13~14의 탄소막 수축과 같거나 덜하였다). 실시예 13(촉매를 사용하지 않음)과 비교할 때 위의 결과는 실시예 4(표 6)에서 관찰될 수도 있다. 또한, 촉매가 첨가되지 않았고 반응물이 펄스로 공급되었을 때(실시예 13)에 얻어진 GPC에 비해, 열적 ALD에서 반응물을 연속적으로 공급하는 동안 촉매가 첨가되었으면, GPC는 상당히 증가되었다(실시예 14 내지 17). 또한, 1 nm의 두께를 갖는 제1 산화막(실시예 16)과 비교하면, 열적 ALD에 의해 증착된 제1 실리콘 산화막의 두께가 3 nm였을 때, 실질적으로 어떠한 막 수축도 검출되지 않았다(실시예 15). 추가적으로, PEALD 공정에 의해서만 증착된 실리콘 산화막(실시예 12)의 등각성, 열적 ALD 공정에 의해서만 증착된 실리콘 산화막(실시예 13과 14)의 등각성 및 열적 ALD와 PEALD의 결합 공정에 의해 증착된 실리콘 산화막(실시예 15~17)의 등각성은 상당히 상이하지 않았다(이들 모두는 90%의 등각성을 초과했다).
실시예 18 내지 21
표 12에 나타낸 특정 조건 및 시퀀스를 갖는 탄소막 없이 산화막이 실리콘 기판 상에 직접 증착되었던 것을 제외하고는 실시예 12 내지 17에 기술된 방식과 실질적으로 동일한 방식으로 실리콘 산화막을 실리콘 기판 상에 형성하였다.
공정 | 시퀀스 | 온도 () |
제1 반응물 | 제1 산화막 두께 (mm) |
|
*18 | PEALD | 도 4 | 400 | - | - |
19 | 열적 + PEALD | 도 6 | 400 | H2O | 3 |
20 | 열적 + PEALD | 도 6 | 400 | H2O | 1 |
21 | 열적 + PEALD | 도 6 | 400 | 에탄올 | 1 |
표 12에서, "*"가 있는 실시예 번호는 비교예(들)를 가리킨다. 얻어진 각각의 막을 평가하였다. 표 13은 평가 결과를 나타낸다.
산화된 Si 기판의 두께 (nm) | 측벽 피복율 (%) |
패턴 로딩 (%) |
열적 ALD GPC (nm/cycle) |
|
*18 | 1.5 | 96 | 93 | - (0.1) |
19 | 0.6 | 96 | 96 | 0.03 |
20 | ~0 | 94 | 97 | 0.03 |
21 | 0.5 | 91 | 93 | 0.02 |
표 13에서, 용어들은 표 8에서 사용된 용어들에 대응한다. "열적 ALD GPC"에서, 괄호 안의 숫자는 PEALD에 의한 GPC를 나타낸다.
표 13에 도시된 바와 같이, 실리콘 산화막이 PEALD에 의해서만 증착되었으면, 하부 실리콘층은 손상되었고 산화되었으며(실시예 18), 반면에 실리콘 산화막이 보호층으로서 열적 ALD에 의해 먼저 증착되었고, 이후 벌크층으로서 PEALD에 의해 연속적으로 증착되었으면, 하부 실리콘층은 훨씬 덜 손상되었고 산화되었다(실시예 19~21). 또한, 촉매가 첨가되지 않았고 반응물이 펄스로 공급되었을 때(표 8의 실시예 7)에 얻어진 GPC에 비해, 열적 ALD에서 반응물을 연속적으로 공급하는 동안 촉매가 첨가되었으면, GPC는 상당히 증가되었다(실시예 21). 또한, 1 nm의 두께를 갖는 제1 실리콘 산화막(실시예 20)과 비교하면, 열적 ALD에 의해 증착된 제1 실리콘 산화막의 두께가 3 nm였을 때, 실질적으로 하부 실리콘층의 어떠한 산화도 검출되지 않았다(실시예 19). 추가적으로, PEALD 공정에 의해서만 증착된 실리콘 산화막(실시예 18)의 등각성 및 열적 ALD와 PEALD의 결합 공정에 의해 증착된 실리콘 산화막(실시예 19~21)의 등각성은 상당히 상이하지 않았다(이들 모두는 90%의 등각성을 초과했다).
상기한 내용을 고려하여, 본원에서 분명하게, 필연적으로, 또는 고유하게 개시된 구현예들에 따라 열적 ALD 및 PEALD의 결합된 연속 공정에 의해서, 플라즈마에 기인하여 하부막을 손상시키지 않고서 고품질의 산화막이 실질적으로 증착될 수 있음을 확인한다.
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 (16)
- 열적 ALD 및 PEALD로 기판 상에 산화막을 증착하기 위한 방법으로서,
반응 챔버에 기판을 제공하는 단계;
상기 반응 챔버 내에서 열적 ALD로 상기 기판 상에 제1 산화막을 증착하는 단계;
진공을 깨뜨리지 않고서, 상기 반응 챔버 내에서 PEALD로 상기 제1 산화막 상에 제2 산화막을 연속적으로 증착하는 단계를 포함하는 방법. - 제1항에 있어서, 상기 열적 ALD의 한 사이클은 전구체를 상기 반응 챔버에 공급하는 단계를 포함하고, 상기 전구체는 아미노실란, 실릴아민, 이소시아네이트실란, 이소토네이트실란、무기 실란, 실란 함유 수산화물, 및 실란 함유 알콕사이드로 구성되는 군으로부터 선택되는 적어도 하나의 화합물의 가스인 방법.
- 제1항에 있어서, 상기 열적 ALD의 한 사이클은 반응물을 상기 반응 챔버에 공급하는 단계를 포함하고, 상기 반응물은 H2O, 에테르, 알콜(예컨대, 메탄올, 에탄올 등), H2 및 O2의 혼합물, 및 H2O2로 구성되는 군으로부터 선택되는 적어도 하나의 가스인 방법.
- 제1항에 있어서, 상기 열적 ALD의 한 사이클은 상기 반응 챔버 내에 제공되는 샤워헤드의 상류에 있는 매니폴드 도관에 반응물을 유입시키고, 상기 반응물을 상기 샤워헤드에서 유입시키고/유입시키거나 상기 반응물을 상기 샤워헤드와 상기 기판이 배치되는 서셉터 사이에 유입시킴으로써 상기 반응물을 상기 반응 챔버에 공급하는 단계를 포함하는 방법.
- 제1항에 있어서, 상기 PEALD의 한 사이클은 연속적으로 흐르는 캐리어 가스를 이용한 펄스로 상기 반응 챔버에 전구체를 공급하는 단계, 및 반응물을 상기 반응 챔버에 연속적으로 공급하는 단계를 포함하는 방법.
- 제5항에 있어서, 상기 반응물은 O2, CO2, 및 N2O로 구성되는 군으로부터 선택되는 적어도 하나의 가스인 방법.
- 제1항에 있어서, 상기 열적 ALD 및 상기 PEALD에 의한 증착을 수행한 후 상기 반응 챔버를 세정하는 단계를 더 포함하는 방법.
- 제7항에 있어서, 상기 세정은, 세정 가스를 전구체와 반응물이 혼합되는 위치의 상류로 공급함으로써 상기 세정 가스를 이용하여 수행되는 방법.
- 제8항에 있어서, 상기 세정 가스는 상기 반응 챔버 상류에서 리모트 플라즈마 유닛에 의해 여기되거나 불소 함유 가스를 사용하여 인-시튜로 여기되는 방법.
- 제1항에 있어서, 상기 열적 ALD의 한 사이클은 상기 사이클을 통하여 반응물을 상기 반응 챔버에 연속적으로 공급하는 단계를 포함하고, 상기 반응물은 에탄올, H2O, 및 O3로 구성되는 군으로부터 선택되는 적어도 하나의 가스인 방법.
- 제1항에 있어서, 상기 열적 ALD의 한 사이클은 펄스로 촉매 가스를 상기 반응 챔버에 공급하는 단계를 포함하고, 상기 촉매 가스는 전구체 및 반응물 이외의 가스이고 상기 사이클에서 상기 산화막의 증착을 촉진시킬 수 있는 방법.
- 제11항에 있어서, 상기 촉매 가스는 피리딘, 알킬 금속, 피리딜실란, 실릴아민, 및 실라잔(silazane)으로 구성되는 군으로부터 선택되는 적어도 하나의 화합물의 가스인 방법.
- 제1항에 있어서, 상기 제1 산화막은 1 내지 7 nm의 두께를 가지고, 상기 제2 산화막은 5 내지 30 nm의 두께를 가지며, 상기 제2 산화막은 상기 제1 산화막보다 두꺼운 방법.
- 제1항에 있어서, 상기 제1 산화막이 증착되는 상기 기판의 표면은 비정질 탄소로 구성되는 방법.
- 제1항에 있어서, 상기 제1 산화막이 증착되는 상기 기판의 표면은 실리콘으로 구성되는 방법.
- 제1항에 있어서, 상기 기판은 패터닝된 리세스들을 가지고, 상기 제1 및 제2 산화막은 상기 리세스들 상에 증착되는 방법.
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US10655221B2 (en) | 2020-05-19 |
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KR102608699B1 (ko) | 2023-11-30 |
TWI756350B (zh) | 2022-03-01 |
CN108411281B (zh) | 2021-12-07 |
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