KR20210117157A - 타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법 - Google Patents
타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법 Download PDFInfo
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- KR20210117157A KR20210117157A KR1020210027117A KR20210027117A KR20210117157A KR 20210117157 A KR20210117157 A KR 20210117157A KR 1020210027117 A KR1020210027117 A KR 1020210027117A KR 20210027117 A KR20210027117 A KR 20210027117A KR 20210117157 A KR20210117157 A KR 20210117157A
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
측면 및 횡방향 면을 갖는 단차에 타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법은, (a) 제1 증착 조건 하에서 상기 기판의 미리 선택된 영역 상에 유전체 층을 증착하는 공정(상기 유전체 층은, 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 대한 저항성이 조정된 부분을 가짐); 및 (b) 공정 (a)에서 수득된 유전체 층을 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 노출시킴으로써 상기 유전체 층의 일부분의 적어도 일부를 제거하고, 이에 의해 상기 기판 상에 상기 타겟 토폴로지 프로파일을 갖는 층 구조를 형성하는 공정을 포함한다.
Description
본 출원은, 일반적으로 기판 상에 형성된 단차에 유전체 막으로 구성된 층 구조를 제조하기 위한 방법에 관한 것이다.
금속 산화물, 질화물 또는 탄화물로 구성된 막과 같은 막의 식각의 경우에 플라즈마 식각이 종종 사용되는데, 그 이유는 식각 속도가 일반적으로 높기(10~100 nm/s) 때문이고, 상기 식각은 이온의 존재로 인해 일반적으로 이방성이다. 이온의 존재는, 재료 간의 식각 선택도를 상대적으로 불량하게 한다. 반면에, 습식 식각은 전형적으로 등방성이고, 종종 식각 선택도를 증가시키지만 웨이퍼 대 웨이퍼 재현성 및/또는 균일성뿐만 아니라 처리량을 감소시킬 수 있다. 또한, 습식 식각은 다량의 화학 폐기물을 생성하므로, 종종 안전 및 환경 문제와 연관이 있어서 문제를 제기한다.
충분한 식각 선택도로 균일한 식각을 달성하기 위해, 라디칼 기반 식각을 효과적으로 사용할 수 있다. 이는, 양호한 선택도를 갖는 건식 식각과 등방성 특성을 갖는 습식 식각의 조합된 이점을 줄 수 있다. 그러나, 이들의 실제 응용예의 경우에, 특정 토폴로지 프로파일을 갖는 원하는 구조를 생성하기 위해, 인접 층에 대해 상이한 재료를 사용할 시 특정 패터닝 계획 및 특정 식각 선택도를 추가로 조사할 필요가 있을 것이다. 라디칼 식각 기술은 미국 특허 제9,064,815호 및 미국 특허 제9,275,834호에 개시된 것과 같이 당업계에 공지되어 있지만, 원하는 토폴로지 프로파일을 갖는 막을 형성하기 위해서는 특히 추가적인 개선이 요구될 것이다.
특히, 습식 식각 화학물질을 사용하는, SiN 막의 선택적 식각은, 반도체 소자의 제조에 널리 사용되어 왔다. 예를 들어, 3D-NAND 소자의 메모리 셀을 제조하기 위해 SiN/SiO2 스택 층의 구조에서 뜨거운(>100°C) 인산 수용액에 의해 SiN 막이 선택적으로 식각된다. 그러나, 식각 속도는 화학 농도, 온도, 및 침지 지속 시간과 같은 여러 파라미터에 따라 달라진다. 또한, 나노미터 수준의 식각 속도에 대한 정밀한 제어는 어렵고, 습식 세정 공정 후에 건조 공정이 필요하기 때문에 공정 처리량은 비교적 낮다. 또한, 습식 식각 화학물질 폐기물은 때때로 건강에 해로우며, 안전 및 환경 문제를 위해 특별히 단단한 습식 세척 수조가 필요하다.
한편, SF6 또는 NF3 플라즈마를 사용하는 건식 식각이 공지되어 있고, 일반적으로 SiN 막 코팅의 측면 잔류 토폴로지 프로파일에 사용된다. 이온의 존재로 인해, 건식 식각은 일반적으로 방향성이며, 이는 이온에 노출된 표면(전형적으로 수평 표면)의 식각 속도를 증가시킨다. 이온의 존재는 종종 등각성 식각 또는 상부 잔류 식각을 달성하는 것을 어렵게 한다. 이러한 이유로, 일부 경우에서 습식 식각은 건식 식각보다 일반적으로 더 자주 사용된다. 미국 특허 제20170345674A1호(NF3/O2를 이용한 건식 식각), 미국 특허 제20180204733A1호(SF6을 이용한 건식 식각), 및 미국 특허 제20120289056A1호(인산을 이용한 습식 식각)를 참조한다.
습식 식각은 일반적으로 미국 특허 제9,754,779B1호에 개시된 방식으로 수행될 수 있으며, 여기서 SiN 막은 제어된 조건 하에서 패터닝된 표면 상에 증착되고, 이어서 이를 dHF 용액을 사용하여 습식 식각함으로써, 측벽 잔류 토폴로지 프로파일 또는 상부/하부 잔류 토폴로지 프로파일 중 하나를 SiN 막 내에 제공한다. 이러한 기술은 화학 물질에 대한 SiN 막의 습식 식각 특성을 이용하며, 여기서 SiN 막의 내화학성은 그의 수평 표면부와 그의 수직 표면부 사이에서 상이하다. 그러나, 개시된 방법에서 패터닝된 구조의 측벽 상에 SiN 막의 일부분을 남기거나 패터닝된 구조의 표면의 상부/하부 상에 SiN 막의 일부분을 남기기 위해서, 자연적으로 상이한 공정인 증착 공정 및 습식 식각 공정은 상이한 처리 챔버에서 각각 수행되어, 고 비용, 저 처리량, 큰 설치 면적, 및 기타 문제를 야기한다.
전술한 바와 같이, 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 이루어지거나 본 출원이 출원된 당시에 알려졌다는 것을 인정하는 것으로 받아들여져서는 아니됨을 알아야 한다.
전술한 바를 고려하여, 일부 구현예는 측면 및 횡방향 면을 갖는 단차로 타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법을 제공하며, 상기 방법은, (a) 제1 증착 조건 하에서 상기 기판의 미리 선택된 영역 상에 유전체 층을 증착하는 공정(상기 유전체 층은, 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 대한 저항성이 조정된 부분을 가짐); 및 (b) 공정 (a)에서 수득된 유전체 층을 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 노출시킴으로써 상기 유전체 층의 일부분의 적어도 일부를 제거하고, 이에 의해 상기 기판 상에 상기 타겟 토폴로지 프로파일을 갖는 층 구조를 형성하는 공정을 포함한다. 상기 타겟 토폴로지 프로파일은 일반적으로 측면 잔류 토폴로지 프로파일, 횡방향 면 잔류 토폴로지 프로파일, 또는 등각성 토폴로지 프로파일일 수 있다.
일부 구현예에서, 상기 방법은, 공정 (a) 이전에, (i) 기준 증착 조건 및 기준 건식 식각 조건을 제공하는 단계(상기 조건 하에서 공정 (a) 및 공정 (b)를 수행함으로써, 기준 토폴로지 프로파일을 갖는 층 구조가 상기 기판 상의 단차에 형성됨); (ii) 이렇게 수득된 기준 토폴로지 프로파일을 타겟 토폴로지 프로파일과 비교할 시, 상기 기판 상의 단차에서 토폴로지 프로파일을 갖는 층 구조를 형성하는 방식으로, 상기 기준 증착 조건 중 적어도 하나의 파라미터 및/또는 상기 기준 건식 식각 조건 중 적어도 하나의 파라미터를 변경하는 단계(상기 토폴로지 프로파일은 상기 기준 토폴로지 프로파일보다 상기 타겟 토폴로지 프로파일에 보다 유사함); (iii) 상기 변경된 증착/건식 식각 조건 하에서 공정 (a) 및 공정 (b)를 수행하는 단계; 및 (iv) 이렇게 수득된 토폴로지 프로파일이 타겟 토폴로지 프로파일과 실질적으로 동등해질 때까지 선택적으로 (ii) 및 (iii) 단계를 반복하는 단계를 추가로 포함한다. 단계 (i) 내지 (iv)를 수행하는 것이 바람직하며, 상기 제1 유전체 층의 내화학성을 참조하여 상기 제2 유전체 층의 내화학성을 적절히 조정하기 위한 제1 증착 조건과 제1 건식 식각 조건을 효율적으로 결정할 수 있게 한다. 그러나, 단계 (i) 및 (iv)의 수행은 공정 (a) 및 (b)를 수행하는 데 특별히 필수적인 것은 아닌데, 그 이유는, "식각 선택도"의 원리가 당업계에 공지되어 있기 때문이고(예, 습식 식각에서의 막의 식각 선택도), 당업자는, 특히 본 개시의 관점에서, 과도한 부담 없이 공정 (a) 및 (b)를 수행하는 데 필요한 조건 및 구조를 결정할 수 있다.
다양한 구현예 중, 제1 예시적인 구현예는, 유전체 층이 상기 기판 상에 증착된 제1 유전체 층, 및 상기 제1 유전체 층 상에 증착되고 이와 접촉하는 제2 유전체 층으로 구성되는 방법을 포함하고, 상기 제2 유전체 층은 상기 제1 유전체 층에 대해 상기 제2 유전체층의 식각 선택도가 적어도 5(예, 적어도 10, 50, 100, 500, 또는 1,000)인 방식으로 불소 및/또는 염소 라디칼에 대해 조정된 저항성을 갖고, 상기 식각 선택도는 상기 제1 건식 식각 조건 하에서 상기 제1 유전체 층의 식각 속도에 대한 상기 제2 유전체 층의 식각 속도의 비율로 정의된다.
상기 방법의 일부 구현예에서, 상기 제1 유전체 층은 산화물 막으로 구성되고, 제2 유전체 층은 실리콘 질화물로 구성된다. 상기 방법의 일부 구현예에서, 제1 유전체 층 및 제2 유전체 층은 동일한 유형이고, 여기서 제1 및 제2 유전체 층을 구성하는 일차 화학적 결합은 동일하다.
제2 예시적인 구현예는, 측면 상에 증착된 유전체 층의 제1 부분, 및 횡방향 면 상에 증착된 유전체 층의 제2 부분이, 제1 및 제2 부분 중 하나의 식각 선택도가 상기 제1 건식 식각 조건 하에서 상기 제1 및 제2 부분 중 다른 것의 식각 속도보다 낮은 식각 속도를 갖고 적어도 1.5(예, 적어도 1.7, 2.0, 2.5, 또는 3.0)인 방식으로, 불소 및/또는 염소에 대해 상이한 저항성을 갖는 방법을 포함하며, 상기 제1 및 제2 부분 중 하나의 식각 선택도는 상기 제1 건식 식각 조건 하에서 상기 제1 및 제2 부분 중 하나의 식각 속도에 대해 상기 제1 및 제2 부분 중 다른 하나의 식각 속도의 비율로 정의된다. 제1 예시적인 구현예에서, 상기 유전체 층은, 상이한 건식 식각 선택도를 갖고 적층된 제1 및 제2 유전체 층으로 구성되는 반면에, 제2 예시적인 구현예에서, 상기 유전체 층은, 상이한 건식 식각 선택도를 갖는 제1 부분(측면 부분) 및 제2 부분(횡방향 부분)으로 구성된다. 그러나, 이들 구현예는 임의의 조합으로 실시될 수 있다.
제3 예시적인 구현예는, 측면 상에 증착된 유전체 층의 일부 및 횡방향 면 상에 증착된 유전체 층의 일부가 상이한 두께를 갖는 방법을 포함한다. 제1 및 제2 예시적인 구현예가, 최종 층 구조의 타겟 토폴로지 프로파일을 달성하기 위해 식각 선택도의 차이를 사용하지만, 제3 예시적인 구현예는 식각 선택도의 차이를 요구하지 않고 최종 층 구조의 타겟 토폴로지 프로파일을 달성할 수 있다. 그러나, 제3 예시적인 구현예는 제1 및/또는 제2 예시적인 구현예(들)와 임의의 조합으로 실시될 수 있다.
제4 예시적인 구현예는 공정 (a) 및 공정 (b)가 동일한 챔버 내에서 수행되는 방법을 포함한다. 상기 방법의 일부 구현예에서, 불소 및/또는 염소 라디칼은 불소 및 질소를 함유하는 가스 및 귀가스로부터, 원격식으로 또는 동일한 챔버 내에서 생성된 불소 라디칼이다. 이러한 예시적인 구현예는 임의의 하나 이상의 개시된 구현예와 조합하여 수행될 수 있다.
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, 예를 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 1은, 예시로서 NF3 원격식 플라즈마 노출 시간과 관련하여 상이한 SiN 막의 식각 두께를 보여주는 그래프이다.
도 2는, 예시로서 HF 습식 식각 노출 시간과 관련하여 상이한 SiN 막의 식각 두께를 보여주는 그래프이다.
도 3은, 예시로서 막 SiN:1의 식각 두께와 비교하여(참조하여) NF3 원격식 플라즈마 식각에서 상이한 SiN 막의 식각 선택도를 보여주는 그래프이다.
도 4a는 상이한 막의 굴절 지수에 대한 막 SiN:1의 식각 속도와 비교하여(참조하여) NF3 원격식 플라즈마 식각에 의한 상이한 SiN 막의 식각 속도를 예시로서 보여주는 그래프이다.
도 4b는 상이한 막의 굴절 지수에 대한 막 SiN:1의 식각 속도와 비교하여(참조하여) HF 습식 식각에 의한 상이한 SiN 막의 식각 속도를 예시로서 보여주는 그래프이다.
도 5는 상이한 SiN 막의 푸리에 변환 적외선(FTIR) 스펙트럼(색상)을 예시로서 나타낸다.
도 6은, 예시로서 SiN 막의 식각 속도 및 Si-N 피크 면적 크기 간의 관계를 보여주는 그래프이다.
도 7은 불소 라디칼을 사용하는 3DNAND 제작에서의 단순화되고 개략적인 공정 시퀀스((a)→(b)→(c)→(d)→(e)→(f))를 예시로서 나타낸다.
도 8a는 불소 라디칼을 사용하여 "계단" 상에 3DNAND를 제작함에 있어서 단순화되고 개략적인 공정 시퀀스((a)→(b)→(c)→(d))를 예시로서 나타낸다.
도 8b는 도 8a의 공정 시퀀스를 사용하여 제조된 최종 구조를 예시로서 나타낸다.
도 9는 불소 라디칼을 사용하여 스페이서 한정 이중 패터링(SDDP) 또는 측벽 스페이서를 형성함에 있어서 개략적이고 단순화된 공정 시퀀스((a)→(b)→(c)→(d))를 예시로서 나타낸다.
도 10은 진공을 파괴하지 않고 클러스터 툴에서 증착과 식각을 조합한 연속 공정 계획을 단순화하여 예시로서 나타낸다.
도 11a는, 예시로서 원격식 플라즈마 공급원이 메인 공정 챔버에 포함된, 원격식 플라즈마 처리 장치의 단순화된 구성을 개략적으로 나타낸다.
도 11b는, 예시로서 원격식 플라즈마가 원격으로 생성되고 반응성 종이 반응 챔버 내로 공급되는 원격식 플라즈마 처리 장치의 단순화된 구성을 개략적으로 보여준다.
도 12a는, 예시로서 상부/하부 제거 계획에 따라 불소 라디칼 식각 후 패터닝된 구조 상에 형성된 실리콘 질화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 12b는, 예시로서 측면 제거 계획에 따라 불소 라디칼 식각 후 패터닝된 구조 상에 형성된 실리콘 질화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 13은, 예시로서 원격식 플라즈마 노출되는 경우에 상이한 산화물 막의 식각 두께를 보여주는 그래프이다.
도 14는, 증착용 RF 플라즈마 공급원 및 건식 식각용 MW 플라즈마 공급원을 갖춘 플라즈마 처리 장치의 개략적인 단순 구성을 예시로서 나타낸다.
도 15는, 예시로서 증착용 장치 및 습식 식각용 다른 장치를 사용하는 공정을 나타낸다.
도 16은, 예시로서 증착 및 건식 식각용 단일 장치를 사용하는 공정을 나타낸다.
도 17은, RF 플라즈마 공급원 및 원격식 플라즈마 공급원을 갖춘 플라즈마 처리 장치의 개략적인 단순 구성을 예시로서 나타낸다.
도 18a는, 예시로서 건식 식각 전("증착 상태")과 건식 식각 후("건식 식각 후")에 형성된 실리콘 질화물 막의 단면도의 주사 투과 전자 현미경(STEM) 사진을 나타낸다.
도 18b는, 도 18a에 나타낸 층 구조를 형성하기 위한 증착 조건 및 건식 식각 조건을 나타낸 표이다.
도 19는, 예시로서 원격식 플라즈마 노출되는 경우에 상이한 TiO 막의 식각 두께를 보여주는 그래프이다.
도 20은, 예시로서 상이한 막의 식각 두께를 보여주는 그래프이다.
도 21a는, 예시로서, 상부/하부 잔여 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 전에 패터닝된 구조 상에 형성된 티타늄 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 21b는, 예시로서, 상부/하부 잔류 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 후에 패터닝된 구조 상에 형성된 티타늄 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 용어 "상부/하부"는 "상부 및/또는 하부"를 지칭하며, 여기서 상단부 및 하단부와 연관된 토폴로지 프로파일은 트렌치의 종횡비에 따라 달라지며, 예를 들어 종횡비가 높을 경우에(예컨대 5 이상), 최종 층 구조는 오직 상부 잔류 토폴로지 프로파일을 가질 수 있다.
도 22a는, 예시로서, 등각성 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 전에 패터닝된 구조 상에 형성된 실리콘 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 22b는, 예시로서, 등각성 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 후에 패터닝된 구조 상에 형성된 티타늄 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 23은, 예시로서, (a) 진공을 파괴하지 않고 클러스터 툴에서 증착 및 식각을 조합하는 개략적이고 단순화된 연속 공정 계획, 및 (b) 동일한 반응기에서 증착 및 식각을 수행하는 개략적이고 단순화된 연속 공정 계획을 나타낸다.
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 1은, 예시로서 NF3 원격식 플라즈마 노출 시간과 관련하여 상이한 SiN 막의 식각 두께를 보여주는 그래프이다.
도 2는, 예시로서 HF 습식 식각 노출 시간과 관련하여 상이한 SiN 막의 식각 두께를 보여주는 그래프이다.
도 3은, 예시로서 막 SiN:1의 식각 두께와 비교하여(참조하여) NF3 원격식 플라즈마 식각에서 상이한 SiN 막의 식각 선택도를 보여주는 그래프이다.
도 4a는 상이한 막의 굴절 지수에 대한 막 SiN:1의 식각 속도와 비교하여(참조하여) NF3 원격식 플라즈마 식각에 의한 상이한 SiN 막의 식각 속도를 예시로서 보여주는 그래프이다.
도 4b는 상이한 막의 굴절 지수에 대한 막 SiN:1의 식각 속도와 비교하여(참조하여) HF 습식 식각에 의한 상이한 SiN 막의 식각 속도를 예시로서 보여주는 그래프이다.
도 5는 상이한 SiN 막의 푸리에 변환 적외선(FTIR) 스펙트럼(색상)을 예시로서 나타낸다.
도 6은, 예시로서 SiN 막의 식각 속도 및 Si-N 피크 면적 크기 간의 관계를 보여주는 그래프이다.
도 7은 불소 라디칼을 사용하는 3DNAND 제작에서의 단순화되고 개략적인 공정 시퀀스((a)→(b)→(c)→(d)→(e)→(f))를 예시로서 나타낸다.
도 8a는 불소 라디칼을 사용하여 "계단" 상에 3DNAND를 제작함에 있어서 단순화되고 개략적인 공정 시퀀스((a)→(b)→(c)→(d))를 예시로서 나타낸다.
도 8b는 도 8a의 공정 시퀀스를 사용하여 제조된 최종 구조를 예시로서 나타낸다.
도 9는 불소 라디칼을 사용하여 스페이서 한정 이중 패터링(SDDP) 또는 측벽 스페이서를 형성함에 있어서 개략적이고 단순화된 공정 시퀀스((a)→(b)→(c)→(d))를 예시로서 나타낸다.
도 10은 진공을 파괴하지 않고 클러스터 툴에서 증착과 식각을 조합한 연속 공정 계획을 단순화하여 예시로서 나타낸다.
도 11a는, 예시로서 원격식 플라즈마 공급원이 메인 공정 챔버에 포함된, 원격식 플라즈마 처리 장치의 단순화된 구성을 개략적으로 나타낸다.
도 11b는, 예시로서 원격식 플라즈마가 원격으로 생성되고 반응성 종이 반응 챔버 내로 공급되는 원격식 플라즈마 처리 장치의 단순화된 구성을 개략적으로 보여준다.
도 12a는, 예시로서 상부/하부 제거 계획에 따라 불소 라디칼 식각 후 패터닝된 구조 상에 형성된 실리콘 질화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 12b는, 예시로서 측면 제거 계획에 따라 불소 라디칼 식각 후 패터닝된 구조 상에 형성된 실리콘 질화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 13은, 예시로서 원격식 플라즈마 노출되는 경우에 상이한 산화물 막의 식각 두께를 보여주는 그래프이다.
도 14는, 증착용 RF 플라즈마 공급원 및 건식 식각용 MW 플라즈마 공급원을 갖춘 플라즈마 처리 장치의 개략적인 단순 구성을 예시로서 나타낸다.
도 15는, 예시로서 증착용 장치 및 습식 식각용 다른 장치를 사용하는 공정을 나타낸다.
도 16은, 예시로서 증착 및 건식 식각용 단일 장치를 사용하는 공정을 나타낸다.
도 17은, RF 플라즈마 공급원 및 원격식 플라즈마 공급원을 갖춘 플라즈마 처리 장치의 개략적인 단순 구성을 예시로서 나타낸다.
도 18a는, 예시로서 건식 식각 전("증착 상태")과 건식 식각 후("건식 식각 후")에 형성된 실리콘 질화물 막의 단면도의 주사 투과 전자 현미경(STEM) 사진을 나타낸다.
도 18b는, 도 18a에 나타낸 층 구조를 형성하기 위한 증착 조건 및 건식 식각 조건을 나타낸 표이다.
도 19는, 예시로서 원격식 플라즈마 노출되는 경우에 상이한 TiO 막의 식각 두께를 보여주는 그래프이다.
도 20은, 예시로서 상이한 막의 식각 두께를 보여주는 그래프이다.
도 21a는, 예시로서, 상부/하부 잔여 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 전에 패터닝된 구조 상에 형성된 티타늄 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 21b는, 예시로서, 상부/하부 잔류 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 후에 패터닝된 구조 상에 형성된 티타늄 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 용어 "상부/하부"는 "상부 및/또는 하부"를 지칭하며, 여기서 상단부 및 하단부와 연관된 토폴로지 프로파일은 트렌치의 종횡비에 따라 달라지며, 예를 들어 종횡비가 높을 경우에(예컨대 5 이상), 최종 층 구조는 오직 상부 잔류 토폴로지 프로파일을 가질 수 있다.
도 22a는, 예시로서, 등각성 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 전에 패터닝된 구조 상에 형성된 실리콘 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 22b는, 예시로서, 등각성 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 후에 패터닝된 구조 상에 형성된 티타늄 산화물 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다.
도 23은, 예시로서, (a) 진공을 파괴하지 않고 클러스터 툴에서 증착 및 식각을 조합하는 개략적이고 단순화된 연속 공정 계획, 및 (b) 동일한 반응기에서 증착 및 식각을 수행하는 개략적이고 단순화된 연속 공정 계획을 나타낸다.
본 개시에서, SiN은 실리콘 질화물 막으로서 특성화되거나 인식되는 막이고, 이는 산소, 탄소, 수소 등 및 실리콘 질화물 막의 특성을 실질적으로 변화시키지 않는 정도까지 불가피한 불순물을 포함하되, SiN 막은 프로세스 레시피에 따라 SiN 막만 아니라, SiNC 막, SiNO 막, SiNCO 막, 또는 기타를 포함하고, 이들 막 명칭은 당업계에서 일반적으로 인정되는 약어이며, 달리 기술되지 않는 한 비화학량론적 방식으로 단지 막 유형(단순히 일차 구성 원소에 의해 표시됨)을 나타낸다. 일부 구현예에서, SiN은 약 2 내지 10, 일반적으로 약 4 내지 8의 유전 상수를 갖는다. 유사하게, SiO 막은 실리콘 산화물 막으로서 특징지워지거나 인식되는 막이고, 이는 질소, 탄소, 수소 등과 같은 다른 원소 및 실리콘 산화물 막의 특성을 실질적으로 변화시키지 않는 한 불가피한 불순물을 포함할 수 있고, SiO 막은 SiO뿐만 아니라, SiOC 막, SiON 막, SiOCN 막 등을 포함한다.
본 개시에서, "단차"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.
일부 구현예에서, 트렌치는 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 nm임), 30 내지 200 nm(전형적으로 50 내지 150 nm)의 깊이, 및 3 내지 20(전형적으로 3 내지 10)의 종횡비를 갖는다.
본 개시에서, "가스"는 증기화된 고체 및/또는 액체를 포함할 수 있으며, 단일 가스 또는 가스 혼합물로 구성될 수 있다. 본 개시에서, 샤워 헤드를 통해 반응 챔버로 유입되는 공정 가스는 전구체 가스 및 첨가 가스로 구성되거나, 본질적으로 이루어지거나, 또는 이루어질 수 있다. 전구체 가스 및 첨가 가스는 보통 혼합 가스로서 또는 개별적으로 반응 공간에 유입된다. 전구체 가스는 귀가스와 같은 캐리어 가스와 함께 유입될 수 있다. 첨가 가스는 반응 가스 및 희석 가스, 예컨대 귀가스로 구성되거나, 본질적으로 이루어지거나, 이루어질 수 있다. 반응 가스 및 희석 가스는 혼합된 가스로서 또는 개별적으로 반응 공간에 유입될 수 있다. 전구체는 둘 이상의 전구체로 구성될 수 있고, 반응 가스는 둘 이상의 반응 가스로 구성될 수 있다. 전구체는 기판 상에 화학 흡착되는 가스이고, 유전체 막의 주 구조체를 구성하는 준금속 또는 금속 원소를 일반적으로 함유하는 가스이고, 증착을 위한 반응 가스는, 가스가 여기되어 기판 상에 원자층 또는 단층을 고정시킬 때 기판 상에 화학 흡착되는 전구체와 반응하는 가스이다. "화학 흡착"은 화학적 포화 흡착을 지칭한다. 공정 가스 이외의 가스, 즉 샤워 헤드를 통과하지 않고 유입되는 가스는, 예를 들면 반응 공간을 밀봉하기 위해 사용될 수 있고, 귀가스와 같은 밀봉 가스를 포함한다. 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 막 또는 층으로 구성될 수 있고, 인접하는 막 또는 층 사이의 경계는 명확하거나 그렇지 않을 수 있으며, 물리적, 화학적, 및/또는 임의의 특성, 형성 공정 및 시퀀스, 및/또는 인접하는 막 또는 층의 기능 또는 목적에 기반하여 구축될 수 있다.
본 개시에서, "어닐링"은 재료를 처리하는 중에 재료가 안정한 형태, 예컨대 성분에 존재하는 말단기(예컨대, 알코올기와 히드록시기)가 더욱 안정한 기(예컨대, Si-Me기)로 치환되고/되거나 더욱 안정한 형태(예컨대, Si-O 결합)를 형성함으로써 막을 조밀화시키는 공정을 지칭한다.
또한, 본 개시에서, "일" 또는 "하나"는 달리 특정되지 않으면, 다수의 종을 포함하는 종 또는 속을 지칭한다. 용어 "의해 구성되는" 및 "갖는"은 일부 구현예에서 "통상적으로 또는 대략적으로 포함하는", "포함하는", "본질적으로 이루어지는", 또는 "~로 이루어지는"을 독립적으로 지칭한다. 또한, 본 개시에서, 임의의 정의된 의미는 일부 구현예에서 반드시 보통의 그리고 관습적인 의미를 배제하는 것은 아니다.
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.
조건 및/또는 구조가 명시되지 않은 본 개시에서, 당업자는 일상적인 실험에 따라 본 개시의 관점으로 이와 같은 조건 및/또는 구조를 용이하게 제공할 수 있다. 개시된 모든 구현예에서, 하나의 구현예에 사용된 임의의 요소는 이와 균등한 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 바람직한 구현예에 제한되지 않는다.
일부 구현예는 불소 라디칼을 사용하여 등각성 식각을 수행하기 위해, 또는 상부 또는 측면 잔류 구조를 생성하기 위해 상이한 금속 함유 재료의 건식 식각을 포함한다. 상이한 금속 화합물 간의 식각 선택도의 차이는, 기판 온도 및 생성된 반응 생성물의 휘발성에 따라 발현되고 달라진다. 따라서, 식각 선택도는 기판 온도 및 반응 화학물질의 적절한 선택에 의해 조정될 수 있다. 본 개시에서, 용어 "금속"은 문맥에 따라 실리콘과 같은 준금속 원소를 포함할 수 있다. 또한, 본 개시에서, 상기 문맥에서 용어 "재료"는 막이 구성되는 원소, 성분, 또는 물질을 지칭하며, 여기서 상이한 재료는 원소적으로 상이한 재료, 원소적으로 동일하지만 조성적으로 상이한 재료, 및 원소적으로 동일하고 조성적으로 동일하지만 상이한 물리적 및/또는 화학적 특성을 갖는 재료를 포함할 수 있다.
상부 및/또는 측면 잔류 구조는 (1) 재료의 증착 조건을 변경한 다음 건식 식각을 거침으로써 생성될 수 있다. 일부 구현예에서, 달성될 수 있는 식각 속도는 0.1 내지 1 nm/s의 범위이며, 양호한 처리량을 유지하면서 식각의 양호한 제어를 가능하게 한다. (2) 건식 식각 조건을 변경하는 것은, 또한 (1)과 조합하여 또는 (1)에 대한 대안으로서 수행될 수 있다. 제안된 건식 식각 공정 흐름은, 또한 동일한 챔버 또는 (다수의 챔버를 갖는) 동일한 클러스터 툴에서 증착 및 식각을 모두 수행하여 측면 또는 상부/하부 잔류 패터닝된 막을 생성하는 것을 가능하게 할 수 있다. 이는 처리량을 증가시키고, 공기에 대한 노출의 결과로서 표면 오염과 관련된 문제를 피할 수 있다.
적층된 재료 특성에 따라 식각 선택도가 달라지기 때문에, 상이한 금속 화합물 및/또는 상이한 고품질 재료(원소적으로 및/또는 조성적으로 동일한 유형의 것을 포함함) 간의 실제 선택도 차이가, 건식 식각 공정과 습식 식각 공정에서 다르게 나타날 수 있다는 사실에도 불구하고, 선택도는 습식 식각에 대한 프록시일 것으로 예상된다. 그러나, 식각 속도 및 웨이퍼-대-웨이퍼 균일성은 건식 식각 공정의 경우에 보다 쉽게 제어 가능하다.
일부 구현예는 불소 라디칼을 사용하여 등각성 식각을 수행하기 위해, 또는 상부 또는 측면 잔류 구조를 생성하기 위해 SiN 막의 고 선택적 건식 식각을 포함한다. 이는, 통상적으로 사용되는 습식 식각 단계를 건식 식각 단계로 대체하는 것을 가능하게 한다. SiN 막의 건식 식각 속도는, 예를 들어 밀도의 함수로서 결정될 수 있다. 습식 식각에서와 같이, 상부 또는 측면 잔류 구조를 생성하기 위해 상이한 막 특성을 갖는 SiN 막 사이의 건식 식각 선택도의 차이가 요구된다. 따라서, 수직 표면 상의 그리고 수평 표면 상의 SiN 막의 밀도를 변화시킴으로써, 원하는 토폴로지 프로파일이 얻어질 수 있다(측면 또는 상부/하부 잔류 또는 이들의 조합). 통상적으로 사용되는 공정을 포함한 건식 식각 공정에서, 산화물(SiO2, TiO2 및 ZrO2)은 또한 이러한 높은 식각 선택도를 나타낼 수 있다.
또한, 제안된 건식 식각 공정은 SiN의 증착 및 식각을 동일한 챔버에서 또는 다수의 챔버를 갖는 동일한 클러스터 툴에서 모두 수행시킬 수 있어, 처리량을 증가시키고 공기에 대한 노출의 결과로서 표면 산화물 형성과 관련된 문제를 피할 수 있다. 또한, 식각 속도 및 웨이퍼-대-웨이퍼 균일성은 습식 식각 공정보다 건식 식각 공정에서 더 쉽게 제어할 수 있다.
추가적으로, 일부 구현예는 단일 챔버 또는 반응기에서 증착 공정 및 건식 식각 공정을 수행하여, 본 개시에서 논의된 문제점 중 적어도 하나를 해결하는 것을 포함한다. 일반적으로, 이러한 방법은, (1) 플라즈마 강화 화학 기상 증착(PECVD) 또는 플라즈마 강화 원자층 증착(PEALD)에 의해 기판의 패터닝된 구조 상에 절연 막을 반응 챔버 내에 증착하는 단계로서, 수평 표면 상에 증착된 막의 일부분과 수직 표면 상에 증착된 막의 일부분은 상이한 내화학성 특성을 갖고(본 개시에서, "수직" 및 "수평", 또는 유사한 단어는 상대적 용어로서 사용되고, 각각 정확한 중력 방향 및 그에 직교하는 정확한 방향으로 제한되도록 의도되지 않으며, 각각 이방성 이온 충돌의 방향 또는 막 두께의 방향에 실질적으로 평행한 임의의 일반적인 방향 및 이에 실질적으로 직교하는 임의의 일반적인 방향으로 지칭됨); 그 다음 (2) 공정 (1)에서 증착된 막을 공정 (1)과 동일한 반응 챔버에서 원격 플라즈마 시스템을 사용하여 원격 플라즈마에 노출시키고, 등방성 건식 식각을 수행하여 막의 일부(타겟 막 유지 부분 이외의 부분)를 제거하고, 이에 의해 상기 막의 일부분을 실질적으로 상기 패턴화된 구조의 측벽 상에만 또는 상기 패턴화된 구조의 상부/하부 표면 상에만 남기는 단계를 포함한다.
개시된 구현예의 일부 양태에서, 제1 및 제2 유전체 층 사이의 식각 선택도의 차이를 이용함으로써 그리고 식각의 방향성을 제어함으로써, 최종 층 구조의 타겟 토폴로지 프로파일을 달성할 수 있는 반면에, 개시된 구현예의 일부 양태에서, 유전체 층의 평면내 식각 선택도의 차이를 이용함으로써, 최종 층 구조의 타겟 토폴로지 프로파일을 달성할 수 있다.
일부 구현예에서, 단지 예시로서 아래 표 1에 나타낸 바와 같이 공정 (a) 및 공정 (b)을 조작함으로써, 증착의 방향성 및 또한 식각의 방향성을 각각 제어함으로써, 표 1에 나타낸 바와 같이 원하는 타겟 토폴로지 프로파일을 달성할 수 있다. 표 1에 나타낸 바와 같이, 일부 구현예에서, 공정 (a) 및 (b)에서 상이한 작동 계획, 또는 상이한 조합은 동일하거나 유사한 최종 토폴로지 프로파일 유형(측면 우세, 등각성, 또는 상부/하부 우세, 그러나 실제 프로파일은 상이할 수 있음)을 초래할 수 있으며, 여기서 최종 층 구조의 토폴로지 프로파일과 관련하여 동일하거나 유사한 결과를 달성하기 위한 다수의 방법(조합)이 존재한다. 표 1에서, "T", "B", 및 "S"는 각각 "상부", "하부", 및 "측면"을 지칭하며, "도 #"는 상응하는계획을 사용하여 형성된 최종 층 구조를 보여주는 도면 번호를 나타낸다. 용어 "등각성"은 일부 구현예에서 약 70% 내지 130%(예, 80% 내지 120%, 90% 내지 110%, 가장 일반적으로 약 100%) 초과와 같이 높은 등각성을 지칭한다. 용어 "우세"는 일부 구현예에서, 적어도 40%, 50%, 100%, 200%, 500%, 1000%, 또는 이들의 임의의 범위만큼 우세와 같이, 의도된 목적을 위해 등각성이지 않거나 재료 차이가 실질적으로 차이가 나는 것을 지칭한다. 또한, 용어 "잔류"는 일부 구현예에서 "우세"의 의미를 지칭한다. 용어 "저 품질"은 일부 구현예에서 기준 품질에 비해 낮은 내화학성, 예를 들어 더 높은 건식 식각 속도, 또는 더 낮은 밀도를 지칭한다. 본 개시에서, 예를 들어 수치 범위를 정의하는 임의의 수는 문맥에 따라, 대표 수, 평균 수, 무작위로 선택된 수, 중간 수, 통상적으로 또는 일반적으로 정의된 수, 또는 이에 상응하는 임의의 수이다.
표 1
전술한 바와 같이, 일부 구현예는 측면 및 횡방향 면을 갖는 단차로 타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법을 제공하며, 상기 방법은, (a) 제1 증착 조건 하에서 상기 기판의 미리 선택된 영역 상에 유전체 층을 증착하는 공정(상기 유전체 층은, 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 대한 저항성이 조정된 부분을 가짐); 및 (b) 공정 (a)에서 수득된 유전체 층을 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 노출시킴으로써 상기 유전체 층의 일부분의 적어도 일부를 제거하고, 이에 의해 상기 기판 상에 상기 타겟 토폴로지 프로파일을 갖는 층 구조를 형성하는 공정을 포함한다. 본 개시에서, 막의 화학적 "저항성"은 주어진 건식 식각 조건 하에서 단위 시간 당 막의 식각된 두께에 기초하여 평가될 수 있고, 제2 막(또는 제2 부분)에 대한 제1 막(또는 제2 부분)의 "식각 선택도"(이는 "식각 속도 선택도"로도 지칭될 수 있음)는 제2 막의 것에 대한 제1 막의 내화학성의 비율에 기초하여 평가될 수 있다.
일부 구현예에서, 상기 방법은, 공정 (a) 이전에, (i) 기준 증착 조건 및 기준 건식 식각 조건을 제공하는 단계(상기 조건 하에서 공정 (a) 및 공정 (b)를 수행함으로써, 기준 토폴로지 프로파일을 갖는 층 구조가 상기 기판 상의 단차에 형성됨); (ii) 이렇게 수득된 기준 토폴로지 프로파일을 타겟 토폴로지 프로파일과 비교할 시, 상기 기판 상의 단차에서 토폴로지 프로파일을 갖는 층 구조를 형성하는 방식으로, 상기 기준 증착 조건 중 적어도 하나의 파라미터 및/또는 상기 기준 건식 식각 조건 중 적어도 하나의 파라미터를 변경하는 단계(상기 토폴로지 프로파일은 상기 기준 토폴로지 프로파일보다 상기 타겟 토폴로지 프로파일에 보다 유사함); (iii) 상기 변경된 증착/건식 식각 조건 하에서 공정 (a) 및 공정 (b)를 수행하는 단계; 및 (iv) 이렇게 수득된 토폴로지 프로파일이 타겟 토폴로지 프로파일과 실질적으로 동등해질 때까지 선택적으로 (ii) 및 (iii) 단계를 반복하는 단계를 추가로 포함한다.
일부 구현예에서, 단계 (ii)에서 변경된 기준 증착 조건 중 적어도 하나의 파라미터는, 공정 (a)가 수행되는 반응 공간에서의 플라즈마 전력, 가스 선택, 가스 유량, 압력 및 온도 중 적어도 하나이다. 일부 구현예에서, 단계 (ii)에서 변경된 기준 건식 식각 조건 중 적어도 하나의 파라미터는 공정 (b)가 수행되는 반응 공간의 적어도 온도이다.
본원에 개시된 기술은 다양한 산업에 광범위하게 적용 가능하고, 상기 측면 및 상기 횡방향 면을 갖는 상기 단차는 측벽을 상기 측면으로서, 그리고 하부면 및 상부면을 횡방향 면으로서 갖는 트렌치로 구성된 응용예; 상기 측면 및 상기 횡방향 면을 갖는 단차는 깊이 방향 면을 상기 측면으로서, 그리고 높이 방향 하부 및 상부면을 횡방향 면으로서 구비한 3D NAND 구조의 일부인 응용예; 및 측면 및 횡방향 면을 갖는 단차가 측면으로서 높이 면 및 횡방향 면으로서 깊이 면을 갖는 계단의 일부인 응용예를 포함하나 이에 제한되지 않는다.
본 개시에서 논의된 바와 같이, 본원에 개시된 기술은 다양한 구현예를 포함하고, 각각의 구현예는 임의의 조합으로 다음 특징부 중 하나 또는 둘 이상을 포함할 수 있다. 또한, 본 개시에서, 명시적으로, 묵시적으로, 또는 내재적으로 개시된 모든 특징부에서, 일 구현예에 사용된 이들 중 임의의 하나 이상은 상호 교환적으로(또는 대안적으로) 사용되거나, 달리 언급되지 않는 한 다른 구현예에서 추가적으로 사용될 수 있거나, 이러한 대체 또는 추가가 가능하지 않거나, 부작용을 야기하거나, 의도된 목적을 위해 작용하지 않는다.
일 양태에서, 구현예는 다음의 특징부 중 적어도 하나 또는 다음의 특징부 중 두 개 이상을 임의의 민감한 조합으로 포함하지만, 이에 제한되지 않는다:
1) 내화학성 또는 식각 선택도의 관점에서 두 개의 상이한 재료(제1 재료 및 제2 재료)를 선택적으로 건식 식각하는 방법으로서, 상기 재료는 기판의 패터닝된 표면 상에 증착되고, 상기 건식 식각 공정은 식각 가스로부터 생성된 불소 및/또는 염소 라디칼에 상기 패터닝된 표면을 등각성 있게 노출시키는 단계를 포함한다.
2) 방법 1)에 있어서, 상기 제1 재료 및 상기 제2 재료의 식각 선택도는 다음에 의해 상이하게 조절된다:
a. 식각 공정 동안의 기판 온도; 및/또는
b. 패턴닝된 표면 상에 증착된 제1 및 제2 재료 각각의 막 품질.
3) 방법 2)에 있어서, 재료 품질은 다음을 포함한 재료 증착 파라미터를 변하시킴으로써 조절된다:
a. RF 전력, 바이어스 전력 등과 같은 플라즈마 조건;
b. 전구체 가스를 포함한 공정 가스의 선택;
c. 공정 가스의 가스 흐름;
d. 증착 공정용 반응 챔버 내 총 가스 압력; 및/또는
e. 증착 공정 동안의 기판 온도.
4) 방법 1)에 있어서, 상기 제1 및/또는 제2 재료가 금속 산화물, 금속 질화물, 금속 탄화물, 또는 이들의 조합(예, TiO, ZrO, TiN, MoO, MoC, TiCO 등)으로 구성된다.
5) 방법 1)에 있어서, 상기 제1 재료는 금속 화합물 재료로 구성되고, 상기 제2 재료는 SiO로 구성된다.
6) 방법 1)에 있어서, 상기 제1 재료는 TiO로 구성되고, 상기 제2 재료는 SiO 또는 SiN으로 구성된다.
7) 방법 1)에 있어서, 상기 제1 재료는 내화학성 측면에서 상기 제2 재료보다 낮은 품질을 갖는다.
8) 방법 1)에 있어서, 상기 공정 가스는 F 및 Ar을 포함한다.
9) 방법 1)에 있어서, 상기 공정 가스는 F, N, 및 O를 포함한다.
10) 방법 1)에 있어서, 상기 공정 가스는 Cl을 포함한다.
11) 방법 1)에 있어서, 상기 라디칼은 다음을 사용하여 생성된다:
a. 원격식 플라즈마 공급원(예, 마이크로파 플라즈마, CCP, ICP); 또는
b. 열 분해 공정(예, 핫 와이어).
12) 방법 1)에 있어서, 상기 식각 공정용 반응 챔버는 상기 증착 공정용 반응 챔버와 클러스터링되고, 상기 증착 공정 및 상기 식각 공정은 진공을 파괴하지 않고 순차적으로 연속적으로 수행된다.
13) 방법 1)에 있어서, 상기 증착 공정 및 상기 식각 공정은 동일한 반응 챔버에서 수행된다.
다른 양태에서, 구현예는 다음의 특징부 중 적어도 하나 또는 다음의 특징부 중 두 개 이상을 임의의 민감한 조합으로 포함하지만, 이에 제한되지 않는다:
1) 다른 재료로 구성된 다른 막에 대한 SiN 막의 고선택성 건식 식각 방법으로서, 막은 기판의 패터닝된 표면 상에 증착되고, 상기 건식 식각 공정은 상기 패터닝된 표면을 식각 가스로부터 생성된 불소 및/또는 염소 라디칼에 등각성 있게 노출시키는 단계를 포함한다.
2) 방법 1)에 있어서, 상기 다른 재료는 막 밀도 및/또는 막 조성과 같은 막 품질 측면에서 상기 SiN 막을 구성하는 SiN과 상이한 SiN이고, 상기 식각 가스는 SF6 또는 NF3과 같은 불소 함유 가스이다.
3) 방법 1)에 있어서, 고도로 선택적인 건식 식각은 패터닝된 표면의 단차 구조 상에 증착된 SiN 막에 수행되고, SiN 막의 원하는 부분은 막 품질의 차이로 인해 SiN 막의 나머지 부분에 대해 선택적으로 제거된다.
4) 방법 1)에 있어서, 상기 다른 재료는 SiO2, SiC, SiCO, Ti 산화물, Hf 산화물, 및/또는 Zr 산화물과 같은 유전체 재료이다.
5) 방법 1)에 있어서, 상기 식각 가스는 F 및 Ar을 포함한다.
6) 방법 1)에 있어서, 상기 식각 가스는 F, N 및 O를 포함한다.
7) 방법 1)에 있어서, 상기 식각 공정은 F 라디칼보다는 Cl 라디칼을 사용한다.
8) 방법 1)에 있어서, 상기 라디칼은 다음을 사용하여 생성된다:
a. 원격식 플라즈마 공급원(예, 마이크로파 플라즈마, CCP, ICP); 또는
b. 열 분해 공정(예, 핫 와이어).
9) 방법 2)에 있어서, 상기 SiN 막을 구성하는 SiN 및 상기 다른 막을 구성하는 SiN의 식각 선택도는, 다음의 공정 조건을 변경함으로써 상이하게 조절된다.
a. RF 전력, 바이어스 전력 등과 같은 플라즈마 조건;
b. 전구체 가스를 포함한 공정 가스의 선택;
c. 공정 가스의 가스 흐름;
d. 증착 공정용 반응 챔버 내 총 가스 압력; 및/또는
e. 증착 공정 동안의 기판 온도.
10) 방법 1)에 있어서, 산화물(SiO, TiO, ZrO)인 상기 다른 막의 식각 선택도에 대한 상기 SiN 막의 식각 선택도는 다음 조건을 변경함으로써 조절된다:
a. 산화물의 막 밀도에 대한 SiN 막의 막 밀도;
b. 전구체 가스를 포함한 공정 가스의 선택;
c. RF 전력, 바이어스 전력 등과 같은 플라즈마 조건;
d. 공정 가스의 가스 흐름;
e. 증착 공정용 반응 챔버 내 총 가스 압력; 및/또는
f. 증착 공정 동안의 기판 온도.
11) 방법 1)에 있어서, 상기 식각 공정용 반응 챔버는 상기 증착 공정용 반응 챔버와 클러스터링되고, 상기 증착 공정 및 상기 식각 공정은 진공을 파괴하지 않고 순차적으로 연속적으로 수행된다.
12) 방법 4)에 있어서, 상기 증착 공정 동안에 상기 공정 온도를 변화시킴으로써, 상기 SiN 및 상기 다른 막의 식각 선택도가 조절된다.
다른 일 양태에서, 구현예는 다음의 특징부 중 적어도 하나 또는 다음의 특징부 중 두 개 이상을 임의의 센스 있는 조합으로 포함하지만, 이에 제한되지 않는다:
1) 기판의 패터닝된 표면 상에 형성된 막의 토폴로지 프로파일을 조절하는 방법으로서, 패터닝된 표면은 수평 표면(전형적으로 오목부의 상부 표면 및 하부 표면) 및 수직 표면(전형적으로 오목부의 측벽)으로 구성된 단차 구조로 구성되며, 상기 방법은, (1) 수평 표면 상에 증착된 막의 일부분 및 수직 표면 상에 증착된 막의 일부분이 상이한 내화학성 특성을 갖는 방식으로 반응 챔버에서 상기 기판의 패터닝된 표면 상에 막을 증착하는 단계; 및 (2) 상기 반응 챔버 내에서 상기 막에 등방성 건식 식각을 수행하되 (a) 상기 수직 표면 상에 증착된 막의 대부분 또는 실질적으로 전부를 남기도록 수평 표면 상에 증착된 막의 일부를 대부분 제거하거나 (b) 상기 수직 표면 상에 증착된 막의 일부를 대부분 제거하여 수평 표면 상에 증착된 막의 부분만 대부분 또는 실질적으로 남기는 방식으로 하는 단계를 포함한다.
2) 방법 1)에 있어서, 상기 등방성 건식 식각은 원격식 플라즈마 시스템을 사용하여 수행된다.
3) 방법 1)에 있어서, 상기 막은 절연막이다.
4) 방법 3)에 있어서, 상기 절연막은 SiN 또는 SiO로 구성된다.
5) 방법 3)에 있어서, 상기 절연막은 용량성 결합 플라즈마(CCP)를 사용하여 증착된다.
6) 방법 4)에 있어서, 상기 절연막은 아미노실란, 할로겐화 실란, 모노실란, 및 디실란으로 이루어진 군으로부터 선택되는 적어도 하나의 전구체를 사용하여 증착된 SiN 막이다.
7) 방법 3)에 있어서, 상기 절연막은 에천트로서 NF3 및/또는 CF4와 같은 불소 함유 건식 가스, 및 Ar, N2, 및/또는 He와 같은 희석 가스를 사용하는 공정 (b)에서 건식 식각을 거친다.
8) 방법 1)에 있어서, 상기 막은 플라즈마 강화 화학 기상 증착(PECVD), 플라즈마 강화 원자층 증착(PEALD), 또는 고밀도 플라즈마 화학 기상 증착(HDPCVD)에 의해 공정 (a)에서 증착되는 방법.
일부 구현예에서, 원격식 플라즈마는 챔버 세정을 위해 통상 또는 종래에 사용되는 공정 (b)에서 막의 건식 식각에 사용된다. 막의 건식 식각용 원격식 플라즈마의 사용은, 높은 생산성, 즉 습식 식각보다 현저하게 높은 높은 식각 속도를 포함한 이점이 크다. 원격식 플라즈마 건식 식각의 식각 속도가 높기 때문에, 원격식 플라즈마 건식 식각의 식각 속도의 제어 가능성을 개선하기 위해, 예를 들어 NF3과 같은 에천트의 농도 또는 유량은 챔버 세정에 일반적으로 사용되는 것보다 낮은 값(예, 10% 내지 90%, 30% 내지 70%, 또는 약 50%)으로 설정될 수 있다. 또한, 막이 트렌치의 표면을 따라 증착되는 경우에, 트렌치의 종횡비는 등방성 건식 식각의 제어 가능성에 영향을 미칠 수 있다. 이러한 문제를 완화시키기 위해, 예를 들어 트렌치에 증착된 막의 상단부/하단부에 대한 측벽 부분의 식각 선택도는, 예를 들어 공정 (a)(증착 공정)에서 증착 압력을 변경함으로써, 이들 부분의 막 품질을 상이하게 조절함으로써 조정될 수 있다.
본 발명의 일부 양태 및/또는 구현예는 예시로서 도면을 참조하여 상세히 설명될 것이지만, 본 발명은 이에 제한되는 것으로 의도되지 않는다.
도 23은 구현예의 일부 양태를 나타내고, (a) 진공을 파괴하지 않고 클러스터 툴에서 증착 및 식각을 조합하는 공정, 및 (b) 동일한 반응기에서 증착 및 식각을 수행하는 공정의 개략적이고 단순화된 연속 공정 계획을 나타낸다. 공정 계획 (a) 중, 단계(S11)에서, 기판이 제공되며("기판 제공"), 상기 기판은 ("수직 면" 또는 "측벽"으로 지칭될 수 있는) 측면 및 ("수평 면" 또는 "상부/하부 면"으로 지칭될 수 있는) 상부면을 갖는, 적어도 하나의 단차로 구성된 패턴 표면을 갖는다. 단계(S12)에서, 기판은 증착을 위해 반응기 챔버(1)로 이송된다("RC 1로 이송"). 기판을 반응 챔버(1)에 전달하기 전에, 제1 유전체 층(예, SiO 재료 또는 다른 산화물 재료로 구성됨)이 기판 상에 이미 형성될 수 있거나, 반응 챔버(1) 내에 형성될 수 있고, 이에 의해 단차 표면은, 제2 유전체층을 반응 챔버(1) 내에서 증착하기 전에 제1 유전체 층으로 구성된다. 단계(S13) 중, 반응 챔버(1)에서, 금속 화합물(본원에서 TiO, TiN뿐만 아니라, 준금속 화합물 및 실리콘 화합물, 예를 들어 SiN을 포함함)로 구성된 제2 유전체 층이, 증착 조건 하에서 제1 유전체 층과 바로 접촉하는 방식으로 제1 유전체 층의 미리 선택된 영역 상에 증착된다("금속 화합물 증착"). 제2 유전체 층은, 제1 유전체 층보다 불소 및/또는 염소 라디칼에 대한 더 낮은 저항성을 갖는다.
단계(S14)에서, 반응 챔버(1)에서 제2 유전체 층의 증착이 완료되면, 기판은 건식 식각용 반응 챔버(2)(상기 챔버는 웨이퍼 핸들링 로봇을 갖는 웨이퍼 이송 챔버에 부착될 수 있고, 상기 반응 챔버(1)도 또한 부착됨)로 이송되어("RC 2로 이송"), 기판이 공기에 노출되지 않고 반응 챔버(2)로 이송될 수 있도록 한다. 단계(S15)에서, 제2 유전체 층은 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 노출됨("라디칼 식각")으로써, 제1 유전체 층을 제거하지 않고 제2 유전체 층의 적어도 일부를 제거하여 기판 상에 토폴로지 프로파일을 갖는 층 구조를 형성한다. 라디칼 식각은 이온(바람직하게는 이온이 실질적으로 없거나 거의 없음)보다는 주로 또는 주로 라디칼을 사용하는 등방성 식각일 수 있으므로, 제2 유전체 층이 등각성이고 균질한(평면내 품질 균일성) 경우에 실질적으로 등각성 식각(즉, 식각의 방향성이 실질적으로 없거나 거의 없음)이 수행될 수 있어 등각성 최종 층 구조를 생성하는 반면에, 제2 유전체 층이 비등각성(예, 상부 우세 증착)이고/이거나 평면내 품질 변화(예, 측면 저품질)를 갖는 경우에 상부 잔류 토폴로지 프로파일 또는 측면 잔류 토폴로지 프로파일을 갖는 최종 층 구조를 생성한다. 라디칼 식각은 습식 식각과 유사하지만 습식 식각보다 식각이 훨씬 더 빠르다.
도 23의 공정 계획 (b)에서, 증착 공정 및 식각 공정은 동일한 반응 챔버에서 수행된다. 이러한 단순화된 공정 계획(증착 + 식각 공정 흐름)은 진공을 파괴하지 않고 SiN 패턴 정의(측면 잔류 또는 상부 잔류)를 가능하게 한다. 공정 계획 (b)에서, 단계(S21, S22, S23, 및 S24)는 공정 계획 (a)의 단계(S11, S12, S13, 및 S15)에 상응하고, 여기서 공정 계획 (b)에서, 단계(S14)에 상응하거나 동등한 단계는 없다.
공정 계획 (b)는 일부 구현예에서, 단지 예시로서 나타낸 다음 반응기 설계를 이용해 달성될 수 있다. 라디칼 식각의 경우, 플라즈마는 반응 챔버 내의 기판과 직접 접촉하지 않는다. 일부 구현예에서, 가능한 플라즈마 공급원은 용량성 결합 플라즈마(CCP), 유도성 결합 플라즈마(ICP), 또는 마이크로파 플라즈마(MWP)일 수 있는 원격식 플라즈마이다. 따라서, 두 개의 전극이 챔버 내에 병렬로 제공되고 기판이 두 개의 전극 사이에 배치되는 인시츄 CCP는 라디칼 식각에 적합하지 않다.
도 11a는, 원격식 플라즈마 공급원이 메인 공정 챔버에 포함된, 원격식 플라즈마 처리 장치의 단순화된 구성을 개략적으로 나타낸다. 도 11b는, 원격식 플라즈마가 원격으로 생성되고 반응성 종이 반응 챔버 내로 공급되는 원격식 플라즈마 처리 장치의 단순화된 구성을 개략적으로 보여준다. 불소 라디칼의 생성은, 예를 들어 유도성 결합 플라즈마(ICP), 용량성 결합 플라즈마(CCP), 또는 마이크로파 플라즈마에 의해 수행될 수 있다. 도 11a 및 도 11b에 나타낸 바와 같이, 인시츄 CCP는 증착을 수행하기 위해, 상부 전극(샤워헤드)(3)과 웨이퍼(W)가 배치되는 하부 전극(서셉터)(1) 사이에 플라즈마를 생성함으로써 사용되며, 여기서 상부 전극(3)은 RF 전력 공급원(5)에 연결되는 반면에 하부 전극(1)은 저주파수 바이어스 공급원(4)에 연결된다. 라디칼 식각을 수행하기 위해, 도 11a에 나타낸 장치는 플라즈마 전력 공급원(6)(예를 들어, RF 전력 공급원 또는 마이크로파 전력 공급원)에 연결된 최상부 전극(2)과 상부 전극(3) 사이에 생성된 간접식 플라즈마(8)를 사용한다. 플라즈마(8)가 최상부 전극(2)과 상부 전극(3) 사이의 공간에 한정되기 때문에, 웨이퍼(W)는 플라즈마에 직접 노출되지 않지만, 상부 전극(3)을 통과하여 공급되고 웨이퍼의 표면(W)에 도달하는 플라즈마의 라디칼에 노출된다. 최상부 전극으로 증착용 공정 가스 및/또는 건식 식각용 에천트 가스를 공급하기 위해 가스 공급 라인(7)이 연결된다.
라디칼 식각을 수행하기 위해, 도 11b에 나타낸 장치는, 에천트 가스가 가스 라인(12)을 통해 공급되고 플라즈마 전력 공급원(9)에 연결된, 원격식 플라즈마 유닛(10) 내부에서 플라즈마(13)를 생성하는 원격식 플라즈마 유닛(10)을 사용한다. 플라즈마(13)가 원격식 플라즈마 유닛(10) 내에 한정되기 때문에, 웨이퍼(W)는 플라즈마에 직접 노출되지 않지만, 상부 플레이트(2')에 연결된 가스 라인(11)을 통해 그리고 상부 전극(3)(샤워헤드)을 통해 공급되고 이동하는 플라즈마의 라디칼에 노출되어, 웨이퍼(W)의 표면에 도달한다. 막의 증착을 수행하는 경우에, 원격식 플라즈마 유닛(10)은 활성화되지 않고, 공정 가스는, 가스 라인(12), 원격식 플라즈마 유닛(10), 가스 라인(11), 및 상부 전극(샤워헤드)(3)을 통해, 상부 전극과 하부 전극 사이의 반응 공간에 공급된다.
도 14는 증착용 RF 플라즈마 공급원과 건식 식각용 MW 플라즈마 공급원이 구비된 플라즈마 처리 장치의 개략적인 단순화 구성을 예시로서 나타내며, 여기서 건식 식각용 MW 플라즈마는 반응 챔버(29)의 측벽 상에 제공된 포트를 통해 서셉터(21) 상에 배치된 반응 공간으로 공급된다. MV 플라즈마는 MW 전력 공급원(24)에 연결된 원격식 플라즈마 유닛(28)에 의해 생성되며, 이를 통해 여기에 공급된 에천트 가스(예, SF6)가 웨이퍼 표면의 건식 식각용 반응 공간에 공급되는 라디칼이 된다. 웨이퍼(W) 상에 막의 증착을 위해, 예를 들어 임의의 적절한 CCP 시스템이 사용될 수 있고, 임의의 적절한 종래의 CCP 시스템을 포함하며, 여기서 RF 전력 공급원(25)과 가스 라인(27)이 최상부 창(22) 상에 제공된 샤워헤드(상부 전극)(23)에 연결된다. 가스 라인(27)은, 증착뿐만 아니라 필요에 따라 건식 식각을 위해 불활성 가스(예, H2, N2, 및/또는 He)를 공급하기 위해 사용된다. 서셉터는 하부 전극으로서 기능하며, 증착을 위해 접지된다. 반응 챔버(29) 내부의 압력은, 고진공을 위해 TMP(터보 분자 펌프)에 연결된 포트(26)를 통해 반응 공간으로부터 가스를 방출함으로써 제어된다.
도 17은, RF 플라즈마 공급원 및 원격식 플라즈마 공급원을 갖춘 플라즈마 처리 장치의 개략적인 단순 구성을 예시로서 나타낸다. 이는 도 11b에 나타낸 장치에서와 같이 원격식 플라즈마 유닛을 사용하는 시스템의 변형이다. 이러한 장치는, 바람직하게는 후술할 시퀀스를 수행하도록 프로그래밍된 제어부와 연결되어 있다. 이 도면에서, 서로 마주하며 평행한 한 쌍의 전기 전도성 평판 전극(44 및 42)을 반응 챔버(43)의 내부(반응 구역)(51)에 제공하고, HRF 전력(13.56 MHz 또는 27 MHz)(60)을 일측에 인가하고 타측(52)을 전기적으로 접지시킴으로써, 플라즈마가 전극들 사이에서 여기된다. 온도 조절기가 하부 스테이지(하부 전극)(42)에 제공되어, 그 위에 놓인 기판(41)의 온도는 주어진 온도로 일정하게 유지된다. 상부 전극(44)은 샤워 플레이트로서의 역할도 수행하며, 반응물 가스(및 귀가스) 및 전구체 가스는 가스 라인(61) 및 가스 라인(62) 각각을 통해, 그리고 샤워 플레이트(44)를 통해 반응 챔버(43)로 유입된다. 추가적으로, 반응 챔버(43)에는 배기 라인(47)을 갖는 원형 덕트(53)가 제공되고, 이를 통해 반응 챔버(43)의 내부(51)에 있는 가스가 배기된다. 추가적으로, 희석 가스가 가스 라인(43)을 통해 반응 챔버(63)로 유입된다. 또한, 반응 챔버(43) 아래에 배치된 이송 챔버(45)는, 이송 챔버(45)의 내부(이송 구역)(56)를 통해 반응 챔버(43)의 내부(51)로 밀봉 가스를 유입하기 위한 밀봉 가스 라인(64)을 구비하며, 반응 구역과 이송 구역을 분리하기 위한 분리 판(54)이 제공된다(웨이퍼가 이송 챔버(45)로 또는 이송 챔버로부터 이송되는 게이트 밸브는 본 도면에서 생략됨). 이송 챔버에는 배기 라인(46)이 또한 구비된다. 일부 구현예에서, 다중 원소 막의 증착 및 표면 처리(들)는 동일한 반응 공간에서 수행되어, 모든 단계들은 기판을 공기 또는 다른 산소 함유 대기에 노출시키지 않고 연속적으로 수행될 수 있다. 일부 구현예에서, 가스를 여기시키기 위한 원격식 플라즈마 유닛이 사용될 수 있다. 웨이퍼의 패터닝된 표면 상에 막 증착이 완료되면, 건식 식각은, 가스 라인(61, 62, 63)의 하류에 있는 샤워헤드(44)에 연결된 가스 라인에 연결되는, 원격 플라즈마 시스템(70)을 사용하기 시작한다. 원격식 플라즈마 시스템(70)으로 에천트 가스 및 불활성 가스가 가스 라인(71, 72)을 통해 각각 공급되어, 에천트 가스가 여기되어, 건식 식각을 위해 반응 구역(51)에 공급되는 라디칼을 포함한 플라즈마를 생성한다.
일부 구현예에서, 도 23의 (b)에 나타낸 일부 구현예에서, 건식 식각은 기판의 단차에서 형성된 층 구조의 토폴로지 프로파일을 조절하기 위해 원격식 플라즈마에 포함된 라디칼을 사용하기 때문에, 증착 공정 및 건식 식각 공정은, 증착 및 건식 식각을 위해 적절한 플라즈마 공급원이 구비된 경우에 동일한 반응 챔버에서 수행될 수 있다. 이러한 장치의 설치 면적은, 증착 및 습식 식각을 위해 종래의 별도의 반응 챔버를 사용하는 경우보다 상당히 작을 수 있고, 건식 식각이 습식 식각보다 훨씬 더 빠르기 때문에(상당히 더 높은 식각 속도를 가짐) 처리량 또한 상당히 개선될 수 있다. 통상적으로, 일부 장치는 챔버 세정을 위한 원격식 플라즈마 유닛이 구비된다. 그러나, 상기 원격 플라즈마 유닛은 챔버 세정을 위해서만 제공되기 때문에, (1) 세정 사이클은 유지 보수를 위해 설정된 세정 일정에 따라 주기적으로 또는 간헐적으로 수행되며, 매 증착 사이클 후에 수행되지 않고, (2) 세정 조건은 가장 효과적으로 내부 벽, 샤워헤드, 및 챔버 내의 서셉터를 세정하기 위해 지속적으로 설정되고, 최종 층 구조의 타겟 토폴로지 프로파일을 달성하도록 기판의 오목부 내에 형성된 개별 층 구조의 토폴로지 프로파일을 구체적으로 조절하도록 전혀 조정되지 않으며, (3) 챔버 세정에 사용된 플라즈마 밀도는 챔버의 내부 표면 상에 형성된 입자 층을 효과적으로 제거하기 위해 높다(상기 입자 층은 종종 가시적이고 따라서 적어도 마이크로미터 수준 제어, 심지어 나노미터 이상 수준 제어를 요구하는데, 그 이유는 상기 입자 층이 마이크로미터 수준 두께(적어도 1 마이크로미터)를 갖기 때문이며, 이는 나노미터 수준 제어(1 마이크로미터 미만 제어, 바람직하게는 100 nm, 50 nm, 20 nm, 10 nm 이하로 조절)를 필요로 하는 막 또는 층의 토폴로지 프로파일을 조절하기에 너무 높은 값임). 또한, 챔버 세정을 위한 적절한 플라즈마 생성 주파수는, 기판의 층 구조의 토폴로지 프로파일을 조절하는 것과 동일하지 않다. 본 발명의 일부 구현예에서, 증착 공정 및 건식 식각 공정 전체가, 최종 층 구조의 타겟 토폴로지 프로파일에 따른 통합 공정으로서 조정되고 제어된다.
도 15는, 예시로서 증착용 장치 및 습식 식각용 다른 장치를 사용하는 공정을 나타낸다. 도 16은, 예시로서 증착 및 건식 식각용 단일 장치를 사용하는 공정을 나타낸다. 도 15 및 도 16에 나타낸 두 가지 공정 계획 모두에서, 증착 공정은 유사하게 수행될 수 있으며, 반응 챔버(도 15의 툴 A, 도 16의 툴 C)에, 트렌치를 갖는 기판(31)이 배치되고, 플라즈마 충돌을 사용함으로써 트렌치에 걸쳐 막 성질의 방향성을 갖는 유전체 막(32)을 형성한다. 막 특성의 방향성은, 수평 표면 상의 막의 일부분과 수직 표면 상의 막의 일부분 사이에서 내화학성(화학적 차이), 밀도(기계적 차이), 두께(구조적 차이), 및/또는 조성(성분 차이)과 같은 특성의 차이를 지칭하지만, 이에 제한되지는 않으며, 이들 모두는 식각 선택도와 연관된다. 임의의 적절한 종래의 방법 또는 본 개시에서 명시적으로, 묵시적으로, 또는 본질적으로 설명된 것을 포함한 임의의 적절한 방법이 사용될 수 있다. 예를 들어, 일부 구현예에서, 2017년 9월 5일에 발행된 미국 특허 제9,754,779호, 2019년 11월 5일에 발행된 미국 특허 제10,468,251호, 및 2020년 1월 7일에 발행된 미국 특허 제10,529, 554호에 개시된 이러한 방법이 사용될 수 있으며, 이들 각각의 개시 내용은 그 전체가 참조로서 본원에 포함된다. 도 15 및 도 16 모두에서, 기판(31) 상에 증착된 막(32)은 등각성이지만, 도 15에서의 습식 식각 특성 및 도 16에서의 건식 식각 특성의 측면에서 방향성을 갖는다.
식각의 경우, 도 15에서, 기판(31)은 다른 반응 챔버(툴 B; 습식 식각 장치)로 이송되어 습식 식각에 의해 상단부/하단부 중 하나를 제거하여 측면 잔류 토폴로지 프로파일(32')을 생성하거나, 막의 측벽 부분을 제거하여 상부/하부 잔류 토폴로지 프로파일(32")을 생성하는 반면에, 도 16에서, 상기 기판(31)은 다른 반응 챔버로 이송되지 않고 동일한 반응 챔버(툴 C, 이중 기능 장치)에 남아 건식 식각에 의해 상단부/하단부 중 하나를 제거하여 측면 잔류 토폴로지 프로파일(32')을 생성하거나, 막의 측벽 부분을 제거하여 상부/하부 잔류 토폴로지 프로파일(32")을 생성한다. 도 16에서, 건식 식각이 동일한 반응 챔버에서 수행되기 때문에, 반응 챔버의 설치 면적은 증가하지 않고, 처리량은 높은(높은 식각 속도 및 전달에 대한 데드타임 없음) 반면에, 도 15에서, 습식 식각이 다른 반응 챔버에서 수행되기 때문에, 두 개의 반응 챔버의 설치 면적은 두 배이고, 처리량은 낮다(낮은 식각 속도 및 전달에 필요한 시간 있음).
일부 구현예에서, 두 개의 층의 효과적인 건식 식각 선택도를 이용하는, 증착 및 건식 식각의 조합된 공정은, 3DNAND 제작에 적절히 적용될 수 있다. 도 7은 불소 라디칼을 사용하는 3DNAND 제작에서의 단순화되고 개략적인 공정 시퀀스((a)→(b)→(c)→(d)→(e)→(f))를 예시로서 나타낸다. 선으로 둘러싸인 구조 (e)는 절연 층(예, SiO2 100)에 대해 높은 원하는 식각 선택도(>예, 1000:1)를 갖는 희생 층(예, SiN 102)의 제거 단계를 나타내며, 여기서 불소 라디칼을 사용하는 본 개시에서 기술된 공정은, 종래의 습식 식각 대신에 이러한 제거 단계 동안에 사용된다. 전형적인 층뿐만 아니라, 층의 전형적인 치수가 예시로서 다음과 같이 표시된다: 100: 절연 층(PECVD에 의해 증착된 SiO2 30 nm 두께); 101: 기판; 102: 희생 층(PECVD에 의해 증착된 SiN 30 nm 두께); 103: 샤넬(SiO2로 충진된 폴리-Si); 104: 금속 컨택(TiN 확산 장벽/W 충진). 이 도면에서, 구조 (a)는 SiO/SiN 스택 형성을 나타내고, 구조 (b)는 직경이 100 nm인 비아 식각을 나타내고, 구조 (c)는 폴리-Si/SiO2로 충진된 비아를 나타내고, 구조 (d)는 비아 식각을 나타내고, 구조 (e)는 희생 층 SiN 제거(NF3/SF6 라디칼 건식 식각)를 나타내고, 구조 (f)는 금속 컨택 형성을 나타낸다.
도 8a는 불소 라디칼을 사용하여 "계단" 상에 3DNAND를 제작함에 있어서 단순화되고 개략적인 공정 시퀀스((a)→(b)→(c)→(d))를 예시로서 나타낸다. 도 8b는 도 8a의 공정 시퀀스를 사용하여 제조된 최종 구조를 예시로서 나타낸다. 선으로 둘러싸인 구조 (d)는 희생 층(예, SiN 203)의 상부 잔류 식각을 나타낸다. 수직 표면(측벽) 상의 희생 층의 막 품질은 수평 표면(상부, 하부) 상의 막 품질보다 상당히 낮기 때문에, 불소 라디칼을 사용하는 경우에 이러한 품질 차이(예, 내화학성의 차이는 밀도 및/또는 조성물 등의 차이에 기인할 수 있음)는 상단부/하단부에 대해 측벽 부분의 선택적 식각을 생성한다. 막의 상단부/하단부와 막의 측벽 부분 사이의 품질 차이는, 본 개시에서 설명된 바와 같이 SiN 막 증착 파라미터를 변경함으로써 제공될 수 있다. 전형적인 층뿐만 아니라, 층의 전형적인 치수가 예시로서 다음과 같이 표시된다: 100: 절연 층(SiO2 30 nm 두께); 101: 기판; 102: 희생 층(PECVD에 의해 증착된 SiN 유형 1 30 nm 두께); 104: 금속 컨택(TiN 확산 장벽/W 충진); 203: 희생 층(NH3 및 DCS를 사용하여 PEALD에 의해 증착된 SiN 유형 2 10 nm 두께); 205: 절연 층(PECVD에 의해 증착된 SiO2 1000 nm 두께); 206: 금속 컨택(TiN 확산 장벽, W 충진). 구조 (a)는 SiN/SiO 스택 형성을 나타내고, 구조 (b)는 계단 형성을 나타내고, 구조 (c)는 희생 층 SiN 증착을 나타내고, 구조 (d)는 SiN(NF3/SF6 라디칼 식각)의 상부 잔류 식각을 나타낸다. 도 8b는 최종 구조까지 추가 처리를 나타낸다.
도 9는 불소 라디칼을 사용하여 스페이서 한정 이중 패터링(SDDP) 또는 측벽 스페이서를 형성함에 있어서 개략적이고 단순화된 공정 시퀀스((a)→(b)→(c)→(d))를 예시로서 나타낸다. 도 8과 유사하게, 측면 잔류 SiN 막이 필요한 응용예도 있다. 측벽 상에 증착된 SiN 막의 일부의 막 밀도 및/또는 품질이 상부 및 하부 상에 증착된 것보다 더 높음을 보장함으로써, 불소 라디칼을 사용하는 경우에 상단부/하단부에 대한 측벽 부분의 식각 선택도가 달성될 수 있다. 조성 차이를 조정하여, 잔류 막의 원하는 두께 및 특성을 달성할 수 있다. 이 기술은 측면 벽 스페이서 형성 또는 스페이서 한정 이중 패턴(SDDP)에 효과적으로 사용될 수 있다. 전형적인 층뿐만 아니라, 층의 전형적인 치수가 예시로서 다음과 같이 표시된다: 300: 기판 재료; 301: 코어 재료; 302: SiN(상부 막 품질(조성 및/또는 밀도)과 상이한 수직 막). 수평 표면(상부, 하부) 상의 막(SiN 302)의 품질은, 수직 표면(측벽)에서의 것보다 상당히 낮다. 이러한 품질 차이(예를 들어, 내화학성의 차이는 밀도 및/또는 조성 등의 차이에 기인할 수 있음)는, 불소 라디칼을 사용하는 경우에 측벽 부분에 대해 상단부의 선택적 식각을 초래한다. 구조 (b)는 패턴 형성을 나타내고, 구조 (c)는 희생 층 SiN 증착을 나타내고, 구조 (d)는 PR 전력을 이용한 NF3 RPU에 의해 SiN의 측면 잔류(상부/하부 우세) 식각을 나타내고(예를 들어, SiO2에 대한 SiN의 높은 식각 선택도, 가령 1000 초과의 값이 얻어짐), 구조 (e)는 코어 식각(선택 사양)을 나타낸다.
도 10은 진공을 파괴하지 않고 클러스터 툴에서 증착과 식각을 조합한 연속 공정 계획을 단순화하여 나타낸다. 이러한 공정 계획은 도 23에서 (a)에 나타낸 것과 실질적으로 동등하며, 여기서 단계(S1, S2, S3, S4, 및 S5)는 도 23에서 (a)의 단계(S11, S12, S13, S14, 및 S15)에 각각 상응하나, 다만 증착된 막이 도 10에서 SiN으로 특히 구성되는 반면에 증착된 막은 도 23에서 금속 화합물로 구성되는 점은 제외한다. 도 23의 (b)에 나타낸 공정 계획은 또한 SiN 막에 적용될 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.
본 발명은 아래의 실행 실시예를 참조하여 더 설명된다. 그러나, 이러한 실시예는 본 발명을 제한하고자 하는 것은 아니다. 조건 및/또는 구조가 명시되지 않는 본 실시예에서, 당업자는 통상적인 실험에 따라 본 개시의 관점으로 이러한 조건 및/또는 구조를 쉽게 제공할 수 있다. 예를 들어, 다음의 예시에서, TiO2, TiN 등으로 구성된 유전체 막을 증착하기 위해 사용되는 임의의 적절한 전구체, 예컨대 2017년 1월 31일에 발행된 미국 특허 제9,556,516호 및/또는 2015년 10월 27일에 발행된 미국 특허 제9,171,716호에 개시된 것들로서, 당업자에 의해 통상적인 실험물로서 선택되고 사용될 수 있으며, 이의 각각의 개시는 그 전체가 참조로서 본원에 포함된다. 또한 예를 들어, 다음의 예시에서, SiO2, SiN 등으로 구성된 유전체 막을 증착하기 위해 사용된 임의의 적절한 전구체, 예컨대 2012년 6월 12일에 발행된 미국 특허 제8,197,915호 및/또는 2017년 11월 21일에 발행된 미국 특허 제9,824,881호에 개시된 것들로서, 당업자에 의해 통상적인 실험물로서 선택되고 사용될 수 있으며, 이의 각각의 개시는 그 전체가 참조로서 본원에 포함된다. 또한, 특정 실시예에 적용된 수치들은 일부 구현예에서 적어도 ±50%의 범위로 수정될 수 있으며, 이러한 수치들은 근사치이다.
실시예
참조예 1
다음 증착 조건 하에서 PEALD에 의해 TiO2 막을 각 기판 상에 증착하였다:
플라즈마: O2 플라즈마 (반응 가스: O2 1000 sccm; 전력: 192 W, 13.56 MHz); 증착 온도: 190°C; 증착 압력: 250 Pa; 막 두께: 24 nm.
다음으로, TiO2 막을 갖는 기판 중 하나를 100°C의 온도에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시키고, TiO2 막을 갖는 기판 중 다른 하나를 200°C의 온도에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. NF3 원격 플라즈마 유닛(PRU)은 다음 조건(이하 "XP5"로 지칭함)으로 설정하였다:
도 19는, 도 19에 표시된 지속 시간 동안 원격식 플라즈마에 노출될 경우에 각각의 TiO2 막의 식각 두께를 보여주는 그래프이다. 도 19에 나타낸 바와 같이, 건식 식각 속도는 플라즈마(라디칼) 노출 시간 및 식각 온도의 함수인 것으로 확인되었다.
참조예 2
TiO2 막을 참조예 1과 동일한 증착 조건 하에서 PEALD에 의해 기판 상에 증착하였다("TiO-1"로 지칭됨). ALD 공정 동안에 전구체의 공급 시간이 TiO-1에 대해 0.05초이고, TiO-2에 대해 0.4초이고, TiO-1의 막 두께가 24 nm이고, TiO-2의 막 두께가 18 nm인 것을 제외하고는, 참조예 1에서와 동일한 증착 조건 하에서 PEALD에 의해 기판 상에 또 다른 TiO2 막("TiO-2"로 지칭됨)을 증착하였다.
다음 증착 조건 하에서 PEALD에 의해 SiO2 막("SiO-1로 지칭됨")을 각 기판 상에 증착하였다:
플라즈마: O2 플라즈마 (반응 가스: O2; 전력: 500 W, 13.56 MHz); 증착 온도: 200°C; 증착 압력: 400 Pa; 막 두께: 30 nm.
증착 온도가 75°C이고 RF 전력이 50 W인 것을 제외하고는 SiO-1과 동일한 증착 조건 하에서 PEALD에 의해 기판 상에 다른 SiO2 막("SiO-2"로 지칭됨)을 증착하였다.
다음으로, TiO-1, TiO-2, SiO-1, 및 SiO-2를 갖는 기판을 40초 동안 200°C의 온도에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. NF3 PRU는 XP5 조건에서 설정하였다.
도 20은 각각의 TiO-1, TiO-2, SiO-1, 및 SiO-2의 식각 두께를 보여주는 그래프이다. 도 20에 나타낸 바와 같이, 식각 선택도는 재료 조성(SiO 또는 TiO) 및 품질(-1 또는 -2)에 따라 달라지는 것으로 확인되었는데, 이는 식각 선택도가 증착 조건을 변경하고/변경하거나 조성을 선택함으로써 조절될 수 있고, 이에 따라 식각 선택도의 광범위한 조작이 가능함을 나타낸다.
실시예 1
TiO2 막을 참조예 1에서와 동일한 방식으로 PEALD에 의해 트렌치를 갖는 기판 상에 증착하였다. 이러한 TiO2 막은 참조예 2의 TiO-1에 상응한다. 도 21a는, 예시로서, 상부/하부 잔류 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 전에 패터닝된 구조 상에 형성된 티타늄 산화물 막(TiO-1)의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 도 21a에 나타낸 바와 같이, TiO-1은 상부-우세 증착 계획으로 증착되었다.
다음으로, TiO-1 막을 갖는 기판을 200°C의 온도에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. NF3 원격 플라즈마 유닛(PRU)을 XP5 조건에서 설정하였다. 도 21b는, 예시로서, 상부 잔류 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 후에 패터닝된 구조 상에 형성된 티타늄 산화물 막(TiO-1)의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 도 21b에 나타낸 바와 같이, NF3 라디칼 식각은 등각성 식각이었으나, 식각 효과에서는 선택적이었고, 여기서 TiO2는 식각되는 반면에 하부 Si는 식각되지 않았다(이는 공정 가스에 산소를 첨가함으로써 층간 산화물에 의해 추가로 보호될 수 있음). NF3 라디칼 식각은 등각성 식각이기 때문에, 상기 상부 우세 증착 계획은 최종 층 구조의 토폴로지 프로파일에 강하게 영향을 끼쳤고, 이는 상부 잔류 토폴로지 프로파일로서, 상기 트렌치 내 및 상기 상부 표면 상에 증착된 TiO-1 막의 모든 부분은 실질적으로 균등하게 또는 균일하게 식각되고, 상기 트렌치의 하부 및 측벽 상에 남아 있는 막이 실질적으로 없는 반면에, 상부 표면 상의 막의 부분은 상부 표면 상의 부분의 두께가 소정의 동일한 정도로 감소하였지만 여전히 남아 있었다. 본 예시는, 최종 층 구조의 상부 잔류 토폴로지 프로파일이, 등각성 식각 계획에 따른 막의 라디칼 식각과 조합하여 상부 우세 증착 계획에 따라 막을 증착함으로써 달성될 수 있음을 나타낸다.
실시예 2
TiO2 막을 참조예 2에서와 동일한 방식으로 PEALD에 의해 트렌치를 갖는 기판 상에 증착하였다. 이러한 TiO2 막은 참조예 2의 TiO-2에 상응한다. 도 22a는, 예시로서, 등각성 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 전에 패터닝된 구조 상에 형성된 티타늄 산화물 막(TiO-2)의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 도 22a에 나타낸 바와 같이, TiO-2은 등각성 증착 계획으로 증착되었다.
다음으로, TiO-2 막을 갖는 기판을 200°C의 온도에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. NF3 원격 플라즈마 유닛(PRU)을 XP5 조건에서 설정하였다. 도 22b는, 예시로서, 등각성 토폴로지 프로파일을 갖는 층 구조를 형성하기 위해 불소 라디칼 식각 후에 패터닝된 구조 상에 형성된 티타늄 산화물 막(TiO-2)의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 도 22b에 나타낸 바와 같이, NF3 라디칼 식각은 등각성 식각이었으나, 식각 효과에서는 선택적이었고, 여기서 TiO2는 식각되는 반면에 하부 Si는 식각되지 않았다(이는 공정 가스에 산소를 첨가함으로써 층간 산화물에 의해 추가로 보호될 수 있음). NF3 라디칼 식각은 등각성 식각이기 때문에, 상기 등각성 증착 계획은 최종 층 구조의 토폴로지 프로파일에 강하게 영향을 끼쳤고, 이는 등각성 토폴로지 프로파일로서, 상기 트렌치 내 및 상기 상부 표면 상에 증착된 TiO-2 막의 모든 부분은 실질적으로 균등하게 또는 균일하게 식각되고, 상기 막 상의 모든 부분의 두께가 소정의 동일한 정도로 감소하였지만 등각성 토폴로지 프로파일을 갖는 최종 층 구조를 생성하였다. 본 예시는, 최종 층 구조의 등각성 토폴로지 프로파일이, 등각성 식각 계획에 따른 막의 라디칼 식각과 조합하여 등각성/균일한 품질 증착 계획에 따라 막을 증착함으로써 달성될 수 있음을 나타낸다.
TiO-1 및 TiO-2는 도 20에 나타낸 바와 같이 사용된 식각 조건에 대해 유사한 식각 속도를 가졌지만, 증착 공정 파라미터 중 적어도 하나(여기서, 전구체의 공급 시간)를 변화시킴으로써, 도 21a(상부 우세 증착) 및 도 22a(등각성 증착)에 나타낸 바와 같이 증착 프로파일이 상이하게 만들어졌다. 조건 및/또는 구조가 본원에 명시되지 않는 다른 증착 프로파일을 형성하기 위해서, 당업자는 일상적인 실험에 따라 본 개시의 관점으로 부담 없이 이러한 조건 및/또는 구조를 쉽게 제공할 수 있다. 등각성 식각(라디칼 식각)과 조합하여, 상이한 증착 프로파일은 도 21b 및 도 22b에 관찰된 바와 같이 상이한 토폴로지 프로파일을 생성한다.
참조예 3
다음 증착 조건 하에서, 다양한 SiN 막(SiN-1 내지 SiN-7) 및 SiO 막을 기판 상에 각각 증착하였다:
SiN-1(PEALD): 증착 온도 450°C; 증착 압력: 3,000 Pa; 플라즈마: N2 플라즈마(반응 가스: N2; 전력: 880 W, 13.56 MHz; 플라즈마 지속시간: 3.3초); 막 두께: 35 nm.
SiN-2(PEALD): 증착 온도 450°C; 증착 압력: 350 Pa; 플라즈마: N2 플라즈마(반응 가스: N2; 전력: 880 W, 13.56 MHz; 플라즈마 지속시간: 3.3초); 막 두께: 50 nm.
SiN-3(PEALD): 증착 온도 100°C; 증착 압력: 350 Pa; 플라즈마: N2 플라즈마(반응 가스: N2; 전력: 115 W, 13.56 MHz; 플라즈마 지속시간: 3.3초); 막 두께: 30 nm.
SiN-4(PEALD): 증착 온도 450°C; 증착 압력: 4 토르; 플라즈마: NH3 플라즈마(반응 가스: NH3; 전력: 100 W, 13.56 MHz); 막 두께: 45 nm.
SiN-5(PEALD): 증착 온도 450°C; 증착 압력: 3 토르; 플라즈마: NH3 플라즈마(반응 가스: NH3; 전력: 125 W); 막 두께: 50 nm.
SiN-6(PRU): 원격 CCP 플라즈마를 사용한 것을 제외하고는 SiN-1에 대한 것과 동일하였다.
SiN-7(LPCVD-SiN; 표준 또는 기준 SiN 막).
SiO(PEALD): SiO-1(참조예 2)에 대한 것과 동일함; 막 두께: 40 nm.
SiN-1, SiN-2, SiN-3, 및 SiN-6은 동일한 제1 전구체를 사용하였고, SiN-4 및 SiN-5는 제1 전구체와 상이한 동일한 제2 전구체를 사용하였다. 증착된 SiN 막의 두께는 25 nm 내지 55 nm 범위였고, 이는 상이한 전구체 및 플라즈마 조건을 갖는 다른 공정 또는 PEALD에 의해 각각 증착되었다. SiN 막(SiN-7)의 표준 샘플을 저압 CVD에 의해 NH3 및 SiH2Cl2로 증착하였다. SiN-7 막의 밀도는 3.18 g/cm3이었다. 여기서의 핵심은 각각의 막이 상이한 밀도 및/또는 상이한 수소 함량 등을 가졌고, 이들 차이는 그의 식각 속도 및/또는 RI(굴절률)를 결정하였다는 것이다. 따라서, 막의 RI는 (도 4a 및 4b에 관련하여 논의된 바와 같이) 식각 속도를 추정하는 데 사용될 수 있다. 조건 및/또는 구조가 본원에 명시되지 않는 이들 막을 증착하기 위해서, 당업자는 일상적인 실험에 따라 본 개시의 관점으로 과도한 부담 없이 이러한 조건 및/또는 구조를 쉽게 제공할 수 있다.
다음으로, 상기 SiN 막을 갖는 각각의 기판을, 챔버 온도가 25°C인 것을 제외하고는 XP5 조건 하에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. SiO 막을 갖는 기판을 NF3 라디칼 대신에 SF6 라디칼에 노출시켰다. SF6 라디칼뿐만 아니라 NF3 라디칼도 SiO 막에 작용한다는 것이 별도의 실험에서 확인되었음을 주목해야 한다.
도 1은, NF3 원격식 플라즈마 노출 시간과 관련하여 상기 상이한 막의 식각 두께를 보여주는 그래프이다. 도 1에서, 상이한 막 밀도 및/또는 상이한 조성을 갖는 다양한 SiN 막의 식각 두께 및 SiO 막의 식각 두께는, NF3 원격 플라즈마 노출 시간의 함수로서 도표화된다. 도 1에 나타낸 바와 같이, 건식 식각 속도는 플라즈마(라디칼) 노출 시간 및 막 품질의 함수인 것으로 확인되었고, 막 품질을 조절함으로써, 막의 건식 식각 속도를 조절하고 타겟층 구조를 형성하기 위해 하나의 막에 대해 하나의 막의 적절한 식각 선택도를 설정할 수 있다.
TiO2, ZrO2 등으로 구성된 막은, SiO2와 유사한 방식으로 PEALD에 의해 증착되었고, SiO2의 것과 유사한 식각 선택도를 나타내었음을 주목해야 한다. 도 13은, 원격식 플라즈마 노출되는 경우에 상이한 산화물 막의 식각 두께를 보여주는 그래프이다.
비교예 1
SiN-1 내지 SiN-6 및 SiO의 막은, 참조예 3에서와 동일한 방식으로 기판 상에 각각 형성되었고, 이어서 참조예 3에서 사용된 라디칼 건식 식각 대신에, 막을 습식 식각(dHF 100:1)하였다.
도 2는, HF 습식 식각 노출 시간과 관련하여 상이한 SiN 막과 SiO 막의 식각 두께를 보여주는 그래프이다. 알 수 있는 바와 같이, NF3 원격식 플라즈마에 대한 SiN 식각 속도는, 습식 식각 속도와 매우 비슷하였다. 또한, NF3 원격식 플라즈마 식각은 선택적이어서, SiO2는 도 1에 나타낸 바와 같이 식각되지 않은 반면에, HF는 도 2에 나타낸 바와 같이 SiO2를 식각하였다.
참조예 4
도 3은, 도 1 및 도 2를 기준으로, 막 SiN-1의 식각된 두께와 비교하여(참조하여) NF3 원격식 플라즈마 식각에서 상기 논의된 상이한 SiN 막의 식각 선택도를 다시 도표화한 그래프이다. 기준 SiN 막에 대한 하나의 SiN 막의 식각 선택도는, 기준 건식 식각 조건 하에서 기준 SiN 막의 식각 속도(또는 식각 두께)에 대한 하나의 SiN 막의 식각 속도(또는 식각 두께)의 비율로 정의된다. 여기서, SiN-1 막을 기준 SiN 막으로서 선택하였다. 도 3에 도시된 바와 같이, SiN-1 막에 대한 SiN 막의 식각 선택도는, SiN-2 내지 SiN-6에 대한 증착 조건을 변화시키는 방식으로 증착 조건을 조절함으로써 조정될 수 있다(SiN 막과 SiN-1 막 간의 조성 차이, 구조적 차이, 물리적 차이, 화학적 차이 등을 초래함). 도 3에 나타낸 바와 같이, SiN 막의 식각 선택도는 NF3 라디칼 식각에 의해 1 내지 50의 범위로 조정될 수 있다. SiO2 막은 NF3 라디칼 식각에 의해 (오차 한계 이내에서) 실질적으로 식각되지 않았으므로, SiO2 막을 기준 막으로서 사용하는 경우에 SiN 막의 식각 선택도는 SiN-1에 대해 적어도 5이고 SiN-2에 대해 적어도 100이었다(즉, SiN-2는 SiO2보다 적어도 100배 더 빠르게 식각됨).
NF3 대신에 원격식 마이크로파 플라즈마(2.45 GHz, 50 W, 2 Pa)에서 생성된 SF6을 사용하여, SiN 막 사이의 식각 속도의 차이가 최대 100까지 더 증가될 수 있다. SiO2 또는 다른 산화물에 대한 SiN 막의 식각 선택도는, (측정 오차를 고려한 후에) SiN-1의 경우 적어도 25, SiN-2의 경우 적어도 4000이었다. 실험 지속 시간이 길수록, 측정 오차가 낮아지고, 이는 식각 선택도가 완벽(무한)에 가까울 가능성이 높다는 것을 의미함을 주목해야 한다.
참조예 5
참조예 3에 설명된 SiN-1 내지 SiN-7로 각각 구성된 SiN 막에 대한 추가 분석을 실시하였고, 이들의 굴절률을 측정하였다. 도 4a는 상이한 막의 굴절 지수에 대한 막 SiN-1의 식각 속도와 비교하여(참조하여) NF3 원격식 플라즈마 식각에 의한 상이한 SiN 막의 식각 속도를 보여주는 그래프이다. 도 4a에 나타낸 바와 같이, 라디칼에 의한 SiN 막의 굴절률 및 이의 건식 식각 속도는 강한 상관 관계(특히, 약 1.95 이하의 굴절률 범위 내에서 굴절률이 감소하는 경우에 식각 속도는 NF3 원격 플라즈마에 대해 선형으로 증가함)를 갖고, 막의 건식 식각 특성은 막 조성 및 밀도 등에 기인하고 이와 연관되기 때문에, 굴절률은 이들의 조성 및 밀도 등을 평가하기 위한 간접 측정으로서 사용될 수 있음을 이해한다. 예를 들어, 다른 막의 것보다 낮은 밀도 및/또는 낮은 품질(열등한 조성)을 갖는 막은, 다른 막의 것보다 낮은 굴절률을 생성한다. 따라서, SiN-6 막의 밀도는 단지 3.18 g/cm3인 것으로 알려져 있지만, SiN-6 막의 것보다 더 낮은 굴절률을 갖는 다른 SiN 막은, SiN-6 막의 것보다 더 낮은 밀도 및/또는 더 낮은 품질(열등한 조성)을 갖는다고 합리적으로 결정할 수 있다.
도 4b는, 상이한 막의 굴절 지수에 대한 막 SiN-1의 식각 속도와 비교하여(참조하여) HF 습식 식각에 의해 상이한 SiN 막(비교예 1에 설명된 바와 같은 SiN-1 내지 SiN-6)의 식각 속도를 보여주는 그래프이다. 도 4b에서 알 수 있는 바와 같이, HF 습식 식각의 경우에 굴절률에 대한 식각 속도의 의존성은, NF3 원격식 플라즈마 식각에 대한 것보다 간단하거나 선형적이지 않았고, 샘플 간의 더 많은 변화가 관찰되었다.
참조예 6
참조예 3에 설명된 SiN-1 내지 SiN-6으로 각각 구성된 SiN 막에 대한 추가 분석을 실시하였고, 이들의 조성/밀도를 분석하였다. 도 5는, 상이한 조성 및 밀도의 상이한 SiN 막의 푸리에 변환 적외선(FTIR) 스펙트럼(컬러)이며, 소광 계수(막의 두께에 대해 정규화된 흡광도)는 파수에 대해 도표화된다. 각 막에서 Si-N, N-H, Si-H, CO2 결합의 존재와 관련된 흡수 피크는, 도 5에 표시되어 있다. Si-N 피크의 상이한 면적 크기는 막 사이의 밀도 차이를 나타내는 반면에, N-H 결합 등의 존재는 이들의 조성에서의 차이를 나타낸다. 모든 결합이 FTIR에 의해 측정될 수 있는 것은 아니며, 이는 조성 차이의 완전한 그림을 제공하지 않는다는 것을 의미함을 주목해야 한다.
도 6은, 도 5에 나타낸 바와 같이 SiN 막의 식각 속도 및 Si-N 피크 면적 크기 간의 관계를 보여주는 그래프이다. 데이터는 SiN 막의 Si-N 결합의 양이 낮을수록(밀도가 낮을수록), 식각 속도가 더 높아짐을 보여준다. 따라서, SiN 막에서 Si-N 결합의 양을 (다양한 증착 공정 파라미터에 의해) 변화시킴으로써, SiN 막의 식각 속도가 조정될 수 있다. 당업자는 과도한 부담 없이 일상적인 실험의 일환으로서, 특히 본원에 개시된 지침에 따라 본 개시의 관점에서 증착 조건을 조절함으로써 식각 속도를 조정할 수 있다.
실시예 3
SiN-4 막을 참조예 3에서와 동일한 방식으로 PEALD에 의해 트렌치(250 nm 깊이, 150 nm 개방 폭)를 갖는 기판 상에 증착하였다. 기판의 상부 표면 상의 SiN-4 막의 두께는 26 nm였다. 또한, SiN-3 막을 참조예 3에서와 동일한 방식으로 PEALD에 의해 트렌치(250 nm 깊이, 150 nm 개방 폭)를 갖는 기판 상에 증착하였다. 기판의 상부 표면 상의 SiN-3 막의 두께는 29 nm였다. SiN-4 막을 사용하는 최종 층 구조의 타겟 토폴로지 프로파일은, 측면 잔류 토폴로지 프로파일인 반면에, SiN-3 막을 사용하는 최종 층 구조의 타겟 토폴로지 프로파일은, 상부/하부 잔류 토폴로지 프로파일이었다.
SiN-4 막에 대한 증착 조건은 다음과 같이, 본 개시에서 논의된 바와 같이 공정 파라미터를 조작함으로써, 상부/하부 저품질(저밀도) 증착을 수행하도록 조정되었다:
(i) 기준 증착 조건 및 기준 건식 식각 조건(여기서는 등각성 식각을 위한 조건 XP5)을 제공하는 단계(여기서, 기준 증착 조건 하에서 PEALD 증착 공정을 수행하고 조건 XP5 하에서 라디칼 식각 공정을 수행하여, 기판의 트렌치를 갖는 표면 상에 기준 토폴로지 프로파일을 갖는 SiN 막이 형성되었음);
(ii) 이렇게 획득된 기준 토폴로지 프로파일을 타겟 토폴로지 프로파일과 비교할 시, 기준 토폴로지 프로파일보다 타겟 토폴로지 프로파일에 보다 가깝게 기판 상의 토폴로지 프로파일을 갖는 층 구조를 형성하는 방식(예, RF 전력 증가 및/또는 공정 압력 감소, 및/또는 상기 전구체 및/또는 상기 반응 가스의 변경)으로 기준 증착 조건 중 적어도 하나의 파라미터를 변화시키는 단계, 및 변경된 증착 조건(건식 식각 조건, 조건 XP5는 변하지 않음) 하에서 PEALD 증착 공정 및 라디칼 식각 공정을 수행하는 단계; 및
(iii) 이렇게 수득된 토폴로지 프로파일이 상기 타겟 토폴로지 프로파일과 실질적으로 근접하거나 동등할 때까지, 단계 (ii)를 반복하는 단계.
유사하게, SiN-3 막에 대한 증착 조건은 본 개시에서 논의된 바와 같이 공정 파라미터를 조작함으로써, 측면 저품질(저밀도) 증착을 수행하도록 조정되었다.
다음으로, SiN-4 막 및 SiN-3 막을 갖는 기판을 각각 25°C의 온도에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. NF3 원격 플라즈마 유닛(PRU)을 XP5 조건에서 설정하였다.
도 12a는, 예시로서 상부/하부 제거 계획에 따라 불소 라디칼 식각 후 패터닝된 구조 상에 형성된 SiN-4 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 도 12b는, 측면 제거 계획에 따라 불소 라디칼 식각 후 패터닝된 구조 상에 형성된 SiN-3 막의 단면도의 주사 전자 현미경(SEM) 사진을 나타낸다. 이들은, 증착 조건 및/또는 증착된 막의 측면 부분과 상단부 사이의 품질(예, 밀도) 차이를 조절함으로써, 건식 식각 후의 최종 층 구조의 토폴로지 프로파일을 조절할 수 있음을 보장한다.
실시예 4 내지 6
도 18b에 나타낸 증착 조건 하에서 PEALD에 의해 트렌치를 갖는 기판 상에 SiN 막 A, B, 및 C를 각각 증착하였다. 각각의 SiN 막의 막 두께를 도 18a에 나타냈다. 도 18a는 또한 SiN 막("증착상태")의 단면 주사 투과 전자 현미경(STEM) 사진을 나타낸다. 도 18a에 나타낸 바와 같이, SiN 막 A는 등각성(89%)인 반면, SiN 막 B 및 C(각각 67% 및 60%의 등각성)는 상부 우세이다. 또한, SiN 막 A 그리고 SiN 막 B 및 C를 측면 저품질 계획 및 상부/하부 저품질 계획에 따라 각각 증착하였으므로, 등각성(등방성) 건식 식각에 노출된 후에 SiN 막 A는 상부 잔류 토폴로지 프로파일을 갖는 반면에, SiN 막 B 및 C는 측면 잔류 토폴로지 프로파일을 갖는다. SiN 막 B와 C 사이의 차이는 막이 증착되는 트렌치의 개방 폭이었고, 여기서 SiN 막 B와 C의 증착 조건은 동일하였지만, 로딩 효과로 인해 막의 등각성은 상이하였다.
다음으로, SiN 막 A, B, 및 C를 도 18b에 나타낸 건식 식각 조건 하에서 NF3 원격 CCP 플라즈마(NF3 라디칼)에 노출시켰다. 최종 층 구조는 도 18a("건식 식각후")에 나타나 있다. 도 18a에 나타낸 바와 같이, SiN 막 A, B, 및 C를 등각성(등방성) 건식 식각에 노출시킴으로써, 이들의 등각성은 89%에서 44%("등각성"에서 "상부 잔류")로, 67%에서 132%("상부 우세"에서 "측면 잔류")로, 및 60%에서 132%("상부 우세"에서 "측면 잔류")로 각각 변하였고, 이는 상기 측벽 상에 증착된 막의 측면 부분과 상기 트렌치의 상부/하부 상에 증착된 막의 횡방향 부분(막 A에서의 "측면-저 품질", 막 B 및 C에서 "상부/하부-저 품질") 사이의 막 품질(밀도 또는 식각 속도)의 차이에 기인하고, 각 막의 측면 부분과 횡방향 부분 사이의 식각 선택도(또는 식각 속도 선택도)의 차이를 초래한다. 이들은, 증착 조건 및/또는 증착된 막의 측면 부분과 횡방향 부분 사이의 품질(예, 밀도) 차이를 조절함으로써, 건식 식각 후 최종 층 구조의 토폴로지 프로파일을 조절할 수 있음을 보장한다.
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 (15)
- 측면 및 횡방향 면을 갖는 단차에서 타겟 토폴로지 프로파일을 갖는 층 구조를 제조하기 위한 방법으로서,
(a) 제1 증착 조건 하에서 상기 기판의 미리 선택된 영역 상에 유전체 층을 증착하는 공정(상기 유전체 층은, 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 대한 저항성이 조정된 부분을 가짐); 및
(b) 공정 (a)에서 수득된 상기 유전체 층을 상기 제1 건식 식각 조건 하에서 불소 및/또는 염소 라디칼에 노출시킴으로써 상기 유전체 층 부분의 적어도 일부를 제거하고, 이에 의해 상기 기판 상에 상기 타겟 토폴로지 프로파일을 갖는 층 구조를 형성하는 공정을 포함하는, 방법. - 제1항에 있어서, 상기 유전체 층이 상기 기판 상에 증착된 제1 유전체 층, 및 상기 제1 유전체 층 상에 증착되고 이와 접촉하는 제2 유전체 층으로 구성되고, 상기 제2 유전체 층은 상기 제1 유전체 층에 대해 상기 제2 유전체 층의 식각 선택도가 5 이상인 방식으로 불소 및/또는 염소 라디칼에 대해 조정된 저항성을 갖고, 상기 식각 선택도는 상기 제1 건식 식각 조건 하에서 상기 제1 유전체 층의 식각 속도에 대한 상기 제2 유전체 층의 식각 속도의 비율로 정의되는, 방법.
- 제2항에 있어서, 상기 제1 유전체 층은 산화물 막으로 구성되고, 상기 제2 유전체 층은 실리콘 질화물 막으로 구성되는, 방법.
- 제2항에 있어서, 상기 제1 유전체 층 및 상기 제2 유전체 층은 동일한 유형이되 상기 제1 및 제2 유전체 층을 구성하는 일차 화학적 결합은 동일한, 방법.
- 제1항에 있어서, 상기 측면 상에 증착된 유전체 층의 제1 부분, 및 상기 횡방향 면 상에 증착된 유전체 층의 제2 부분이, 상기 제1 및 제2 부분 중 하나의 식각 선택도가 상기 제1 건식 식각 조건 하에서 상기 제1 및 제2 부분 중 다른 것의 식각 속도보다 낮은 식각 속도를 갖고 1.5 이상인 방식으로, 불소 및/또는 염소에 대해 상이한 저항성을 갖되, 상기 제1 및 제2 부분 중 하나의 식각 선택도는, 상기 제1 건식 식각 조건 하에서 상기 제1 및 제2 부분 중 하나의 식각 속도에 대한 상기 제1 및 제2 부분 중 다른 하나의 식각 속도의 비율로 정의되는, 방법.
- 제1항에 있어서, 상기 측면 상에 증착된 유전체 층의 일부 및 상기 횡방향 면 상에 증착된 유전체 층의 일부가 상이한 두께를 갖는, 방법.
- 제1항에 있어서, 상기 타겟 토폴로지 프로파일은 측면 잔류 토폴로지 프로파일, 횡방향 면 잔류 토폴로지 프로파일, 또는 등각성 토폴로지 프로파일인, 방법.
- 제1항에 있어서, 공정 (a) 및 공정 (b)는 동일한 챔버에서 수행되는, 방법.
- 제8항에 있어서, 상기 불소 및/또는 염소 라디칼은 불소와 질소를 함유한 가스 및 귀가스로부터, 원격식으로 또는 동일한 챔버 내에서 생성된 불소 라디칼인, 방법.
- 제1항에 있어서, 공정 (a)를 시작하기 전에,
(i) 기준 증착 조건 및 기준 건식 식각 조건을 제공하는 단계(상기 조건 하에서 공정 (a) 및 공정 (b)를 수행함으로써, 기준 토폴로지 프로파일을 갖는 층 구조가 상기 기판 상의 단차에 형성됨);
(ii) 이렇게 수득된 상기 기준 토폴로지 프로파일을 상기 타겟 토폴로지 프로파일과 비교할 시, 상기 기판 상의 단차에서 토폴로지 프로파일을 갖는 층 구조를 형성하는 방식으로, 상기 기준 증착 조건 중 적어도 하나의 파라미터 및/또는 상기 기준 건식 식각 조건 중 적어도 하나의 파라미터를 변경하는 단계(상기 토폴로지 프로파일은 상기 기준 토폴로지 프로파일보다 상기 타겟 토폴로지 프로파일에 보다 유사함);
(iii) 상기 변경된 증착/건식 식각 조건 하에서 공정 (a) 및 공정 (b)를 수행하는 단계; 및 선택적으로
(iv) 이렇게 수득된 상기 토폴로지 프로파일이 상기 타겟 토폴로지 프로파일과 실질적으로 동등해질 때까지 (ii) 및 (iii) 단계를 반복하는 단계를 추가로 포함하는, 방법. - 제10항에 있어서, 단계 (ii)에서 변경된 기준 증착 조건 중 적어도 하나의 파라미터는, 공정 (a)가 수행되는 반응 공간에서의 플라즈마 전력, 가스 선택, 가스 유량, 압력 및 온도 중 적어도 하나인, 방법.
- 제10항에 있어서, 단계 (ii)에서 변경된 상기 기준 건식 식각 조건 중 적어도 하나의 파라미터는, 공정 (b)가 수행되는 반응 공간의 적어도 온도인, 방법.
- 제1항에 있어서, 상기 측면 및 상기 횡방향 면을 갖는 단차는, 상기 측면으로서 측벽을 갖고, 상기 횡방향 면으로서 하부면 및 상부면으로 구성되는, 방법.
- 제1항에 있어서, 상기 측면 및 상기 횡방향 면을 갖는 단차는, 상기 측면으로서 깊이 방향 면과 상기 횡방향 면으로서 높이 방향 하부 및 상부면을 갖는 수평 오목부를 구비한 3D NAND 구조의 일부인, 방법.
- 제1항에 있어서, 상기 측면 및 상기 횡방향 면을 갖는 단차는, 상기 측면으로서 높이 면을 갖고, 상기 횡방향 면으로서 깊이 면을 갖는 계단의 일부인, 방법.
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