KR20180009702A - 텅스텐의 선택적 퇴적 - Google Patents

텅스텐의 선택적 퇴적 Download PDF

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KR20180009702A
KR20180009702A KR1020170087308A KR20170087308A KR20180009702A KR 20180009702 A KR20180009702 A KR 20180009702A KR 1020170087308 A KR1020170087308 A KR 1020170087308A KR 20170087308 A KR20170087308 A KR 20170087308A KR 20180009702 A KR20180009702 A KR 20180009702A
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metal
substrate
film
tungsten
precursor
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알렉세이 와이. 코발진
멩디 양
안토니우스 에이. 아이. 아르닝크
로프 에이. 엠. 볼테르스
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에이에스엠 아이피 홀딩 비.브이.
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Abstract

기판 상으로 금속 막을 선택적으로 퇴적하는 방법이 개시된다. 구체적으로, 상기 방법은 상기 기판 상으로 금속 전구체를 흘리는 단계와, 상기 기판 상으로 비금속 전구체를 흘리는 한편, 상기 비금속 전구체를 핫 와이어와 접촉시키는 단계를 포함한다. 구체적으로, 텅스텐 전구체 및 수소 전구체 사이의 반응은 텅스텐 막을 선택적으로 형성하며, 여기서 상기 수소 전구체가 텅스텐 핫 와이어에 의해 여기된다.

Description

텅스텐의 선택적 퇴적{Selective deposition of tungsten}
[1] 본 개시는 2016년 7월 19일 출원된 "Selective Deposition of Tungsten"이라는 명칭의 미국 임시 특허 출원 번호 제62/364,185호와, 2016년 10월 28일 출원된 "Selective Deposition of Tungsten"이라는 명칭의 미국 임시 특허 출원 번호 제62/414,408호의 이익을 주장하며, 이들 모두 참조문헌으로서 병합된다.
[2] 본 개시는 일반적으로 전자 소자들의 제조 공정들에 관한 것이다. 더욱 구체적으로는, 본 개시는 핫 와이어(hot wire) 시스템을 사용한 사이클(cyclic) 노출 또는 원자층 퇴적(atomic layer deposition, ALD)을 통한 선택적 퇴적에 관한 것이다. 특히, 본 개시는 핫 와이어 사이클 노출 공정을 통한 텅스텐 막들의 형성에 관한 것이다.
[3] 디실레인(Si2H6) 및 텅스텐 헥사플루오라이드(WF6)를 전구체들로서 사용하여 텅스텐을 선택적으로 퇴적하는 공정들이 존재한다. Haukka et al.의 미국 특허 번호 제8,956,971호는 이러한 공정을 개시하며, 여기서 대략 150℃의 온도에서 퇴적이 발생한다. 퇴적은 구리 표면 상에 형성되는 텅스텐층을 유발할 수 있다.
[4] 플라즈마를 통해 텅스텐을 형성하기 위한 접근법들은 선택비에 대한 플라즈마의 악영향에 기인하여 실행 가능하지 않았다. 구체적으로, 플라즈마는 다수의 표면들 상에 막들을 형성하는 경향이 있고, 다른 표면들 사이를 구별하지 않는다.
[5] 텅스텐 막들의 형성은 일렉트로마이그레이션(electromigration, EM) 저항성을 향상시키도록 사용될 수 있다. EM 저항성은 유전 확산 배리어 및 금속성 물질 사이의 계면 상부에 금속 캡을 형성함에 의해 달성될 수 있다. 그러나 유전 표면에 대하여 금속성 표면들 상에 우수한 선택비를 달성하는 것은 어려웠다. 요구되는 표면 터미네이션들을 얻기 위하여 열적 또는 래디칼 처리를 포함하는 가벼운 표면 처리들과 같은 몇몇의 접근법들이 취해져 왔다. 그러나 가벼운 표면 처리들은 선택적 퇴적을 위하여 요구되는 표면을 적절하게 준비하지 못할 수 있다.
[6] 그 결과로, 높은 선택비를 가지며 텅스텐 또는 다른 금속 막을 퇴적하는 공정이 요구된다.
본 발명의 목적은 전술한 문제들을 극복하기 위한 것이다.
[7] 본 발명의 적어도 하나의 실시예에 따르면, 텅스텐 막의 선택적 형성 방법이 개시된다. 상기 방법은, 반응 챔버 내에 공정을 위한 제1 표면과 제2 표면을 포함하는 기판과, 가스의 여기된 종들을 생성하기 위한 핫 와이어를 제공하는 단계; 상기 기판 상으로 텅스텐 전구체 펄스/퍼지 단계를 수행하는 단계로서, 상기 기판 상으로 텅스텐 전구체를 펄스하는 단계와, 상기 반응 챔버로부터 여분의 상기 텅스텐 전구체를 퍼지하는 단계를 포함하는, 상기 텅스텐 전구체 펄스/퍼지 단계를 수행하는 단계; 및 상기 기판 상으로 수소 전구체 펄스/퍼지 단계를 수행하는 단계로서, 상기 기판 상으로 상기 핫 와이어에 의해 여기된 수소 전구체를 펄스하는 단계와, 상기 반응 챔버로부터 여분의 상기 수소 전구체를 퍼지하는 단계를 포함하는, 상기 수소 전구체 펄스/퍼지 단계를 수행하는 단계;를 포함하며, 상기 텅스텐 전구체는 텅스텐 헥사플루오라이드(WF6) 중 적어도 하나를 포함하고, 상기 수소 전구체는 수소(H2) 중 적어도 하나를 포함하며, 상기 핫 와이어의 온도는 약 1000℃ 이상이고, 텅스텐 막이 상기 제1 표면 상에 선택적으로 형성된다.
[8] 본 발명의 적어도 하나의 실시예에 따르면, 금속을 포함하는 막의 선택적 형성 방법이 개시된다. 상기 방법은, 반응 챔버 내에 공정을 위한 기판과, 적어도 가스를 접촉하기 위한 핫 와이어 성분을 제공하는 단계; 상기 기판을 금속 전구체에 노출시키는 단계; 및 상기 기판을 상기 핫 와이어의 인접부에 노출되었던 가스에 노출시키는 단계를 포함하고, 상기 기판은 적어도 두 개의 다른 물질들을 포함하며, 상기 금속막이 상기 표면들 중 하나 내에 선택적으로 형성된다.
[9] 본 발명의 적어도 하나의 실시예에 따르면, 텅스텐 막의 형성 방법이 개시된다. 상기 방법은, 반응 챔버 내에 공정을 위한 기판과, 상기 반응 챔버를 통해 적어도 가스를 통과시키기 위한 핫 와이어를 제공하는 단계; 상기 기판 상으로 텅스텐 전구체를 흘리는 단계; 및 상기 기판 상으로 수소 전구체를 흘리는 단계를 포함하고, 상기 수소 전구체는 상기 핫 와이어와 접촉하며, 상기 텅스텐 전구체와, 상기 핫 와이어와 접촉한 상기 수소 전구체 사이의 반응이 텅스텐 막을 형성하며, 상기 반응 챔버는 핫-월 반응 챔버이다.
[10] 본 발명 및 종래 기술에 대비하여 얻어지는 이점들을 요약하기 위한 목적들로서, 본 발명의 특정한 목적들 및 이점들이 여기서 위에 설명되었다. 물론, 본 발명의 임의의 특정한 실시예에 따라 이러한 목적들 또는 이점들 모두가 필수적으로 달성될 필요는 없음이 이해되어야 한다. 따라서, 예를 들어 당업자들은 본 발명이 여기서 개시되거나 제안될 수 있는 다른 목적들 또는 이점들을 필수적으로 달성하지 않고, 여기서 개시되거나 제안된 하나의 이점 또는 일군의 이점들을 달성하거나 최적화하는 방식으로 구체화되거나 수행될 수 있다는 점을 인식할 것이다.
[11] 이러한 실시예들 모두는 여기 개시된 본 발명의 범위 내에 속할 것이 의도된다. 이러한 및 다른 실시예들은 첨부된 도면들을 참조로 하는, 하기의 특정한 실시예들의 상세한 설명으로부터 당업자들에게 즉각적으로 명백해질 것이며, 본 발명이 개시된 임의의 특정 실시예(들)에 제한되는 것은 아니다.
[12] 여기 개시된 본 발명의 이러한 및 다른 특징들, 태양들 및 이점들은 특정한 실시예들의 도면들을 참조로 아래에서 설명되나, 도면들은 본 발명을 도시하도록 의도되며, 본 발명을 제한하도록 의도되지 않는다.
[13] 도 1은 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다.
[14] 도 2는 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다.
[15] 도 3은 본 발명의 적어도 하나의 실시예에 따른 방법 단계를 도시한다.
[16] 도 4는 본 발명의 적어도 하나의 실시예에 따른 방법 단계를 도시한다.
[17] 도 5a 및 도 5b는 본 발명의 적어도 하나의 실시예에 따른 구조물의 상면도를 도시한다.
[18] 도 6a 및 도 6b는 본 발명의 적어도 하나의 실시예에 따른 구조물의 단면도를 도시한다.
[19] 도 7은 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다.
[20] 도 8은 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다.
[21] 도 9는 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다.
[22] 도 10은 본 발명의 적어도 하나의 실시예에 따른 구조물의 단면도를 도시한다.
[23] 도 11은 본 발명의 적어도 하나의 실시예에 따른 구조물의 단면도를 도시한다.
[24] 특정한 실시예들 및 실험예들이 아래에 개시되었지만, 본 발명이 특정하게 개시된 실시예들 및/또는 본 발명의 용법들 및 이들의 명백한 개조들 및 등가물들을 넘어 연장됨이 당업자에 의해 이해될 것이다. 따라서, 개시된 본 발명의 범위는 아래에 설명된 특정하게 개시된 실시예들에 의해 제한되어서는 안됨이 의도된다.
[25] 막의 퇴적은 핫 와이어를 따라, 및 그 가까운 인접부 내에서 흐르는 흘려진 전구체 가스로부터 래디칼 종들을 생성하도록 상기 핫 와이어 또는 가열 필라멘트를 사용한 장치를 사용하여 일어날 수 있다. 이러한 장치는 미국 특허 출원 번호 제2013/0337653 A1호에 개시되며, 이는 참조문헌으로서 병합된다. 다른 가열 필라멘트들은 미국 특허 출원 번호 제2014/0120723 A1호에 개시된다. 상기 장치는 반응 챔버, 기판 홀더, 가스 소스, 및 핫 와이어를 따라 흐르는 가스로부터 래디칼들을 생성하기 위한 상기 핫 와이어 또는 가열 필라멘트, 기판 홀더를 가열하기 위한 히터, 및 반응 챔버의 벽들을 가열하기 위한 히터를 포함할 수 있다.
[26] 반응 챔버 내에서, 기판 홀더는 기판을 홀드하도록 배치된다. 가스 소스는 반응 챔버 내부로 전구체 가스를 제공할 수 있다. 또한 반응 챔버 내에서, 핫 와이어 또는 가열 필라멘트가 존재할 수 있다. 핫 와이어 또는 가열 필라멘트는 와이어, 리본, 또는 중앙의 종축 주위로 나선형으로 연장되는 복수의 와인딩들을 포함하도록 코일 내로 감겨진 유사한 구조들을 포함할 수 있다. 핫 와이어 또는 가열 필라멘트는 텅스텐과 같은 금속, 또는 1000℃ 이상, 1200℃ 이상, 1300℃ 이상, 또는 1500℃ 이상의 온도를 견딜 수 있는 다른 적합한 물질을 포함할 수 있다. 적어도 하나의 실시예에 따르면, 흘려진 가스는 핫 와이어 또는 가열 필라멘트와 직접 접촉하게 될 수 있고, 이는 흘려진 가스를 분쇄함(cracking)에 의해 공정을 촉매한다.
[27] 전구체 가스는 핫 와이어 또는 가열 필라멘트와 접촉하게 될 수 있고, 이후 전구체 가스 래디칼들을 형성하도록 분해하며, 이는 이후 기판 상으로 흡착하거나 또는 기판 상의 흡착된 전구체와 반응할 수 있다.
[28] 기판은 다양한 종류들의 물질들을 포함할 수 있다. 집적 회로들을 제조할 때, 기판은 일반적으로 달라지는 화학적 및 물리적 특성들을 갖는 다수의 박막들을 포함한다. 예를 들어, 기판은 실리콘-함유층과 금속층을 포함할 수 있으나, 한정되는 것은 아니다. 일부 실시예들에서, 기판은 금속 카바이드를 포함할 수 있다. 일부 실시예들에서, 기판은 도전성 산화물을 포함할 수 있다. 일부 실시예들에서, 기판은 실리콘 및 약 100 mm 내지 약 450 mm, 약 200 내지 약 300 mm의 직경을 갖는 반도체 웨이퍼이다. 다른 실시예들에서, 기판은 유리; 반도체들; 화합물 유사 반도체들, 예를 들어 III-V 또는 II-VI 반도체들; 및 비평면 또는 평면 기판들과 같은 다양한 다른 종류들의 기판들과 같은 다른 종류들의 기판들을 포함할 수 있다.
[29] 적어도 하나의 실시예에서, 기판은 여기서 제1 금속 표면 또는 제1 금속성 표면으로 지칭되는 금속을 포함하는 제1 표면을 구비할 수 있다. 제1 표면은 본질적으로 Cu 또는 Co와 같은 금속 원소일 수 있다. 다른 실시예들에서, 제1 표면은 금속 질화물 또는 전이 금속을 포함할 수 있다. 전이 금속은 Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir 및 Pt의 군으로부터 선택될 수 있다. 일부 실시예들에서, 제1 표면은 예를 들어 Au, Pt, Ir, Pd, Os, Ag, Re, Rh, 및 Ru와 같은 귀금속을 포함할 수 있다. 다른 실시예들에서, 금속막은 다른 표면들에 대하여 금속 산화물 표면 상에 선택적으로 퇴적될 수 있고, 여기서 금속 산화물 표면은 예를 들어 WOx, HfOx, TiOx, AlOx, 또는 ZrOx 표면일 수 있다. 일부 실시예들에서, 금속 산화물 표면은 금속성 물질의 산화된 표면일 수 있다.
[30] 적어도 하나의 실시예에서, 기판은 제2 표면, 바람직하게는 실리콘-함유 표면이고, 여기서 제2 실리콘-함유 표면 또는 실리콘을 포함하는 제2 표면으로 지칭되는 제2 표면을 구비할 수 있다. 일부 실시예들에서, 실리콘-함유 표면은 예를 들어 SiO2를 포함할 수 있다. 일부 실시예들에서, 실리콘-함유 표면은 Si-O 결합들을 갖는 물질, 예를 들어 SiO2 또는 SiO2계 로우-k(low-k) 물질을 포함할 수 있다. 일부 실시예들에서, 제2 표면은 실리콘 산화물, 실리콘 질화물, 실리콘 카바이드, 실리콘 산질화물, 실리콘 이산화물 또는 이들의 혼합물들을 포함할 수 있다. 일부 실시예들에서, 제2 표면을 포함하는 물질은 다공성 물질일 수 있다. 일부 실시예들에서, 다공성 물질은 서로 연결되는 기공들(pores)을 함유할 수 있는 한편, 다른 실시예들에서 기공들은 서로 연결되지 않는다. 일부 실시예들에서, 제2 표면은 약 4.0 이하의 유전상수 또는 상대 유전율(relative permittivity)를 갖는 절연체로 정의되는 로우-k 물질을 포함할 수 있다. 일부 실시예들에서, 로우-k 물질의 유전상수 또는 상대 유전율은 약 3.5 이하, 약 3.0 이하, 약 2.5 이하, 또는 약 2.3 이하일 수 있다.
[31] 본 발명의 실시예들은 금속성 막들, 전이 금속들을 포함하는 막들, 또는 전이 금속들을 포함하는 금속성 막들을 선택적으로 형성하는 것에 관한 것일 수 있다. 일부 실시예들에서, 막들은 원소 주기율표의 IV, V, 또는 VI 족 원소들을 포함하는 금속 또는 금속성 막을 포함할 수 있다. 일부 실시예들에서, 막들은 원소 주기율표의 V 또는 VI 족 원소들을 포함하는 금속 또는 금속성 막을 포함할 수 있다. 일부 실시예들에서, 막들은 원소 주기율표의 VI 족 원소들을 포함하는 금속 또는 금속성 막을 포함할 수 있다. 일부 실시예들에서, 막들은 텅스텐 또는 몰리브덴을 포함하는 막들일 수 있다. 본 발명의 실시예들은 텅스텐 또는 몰리브덴의 형성을 유발할 수 있다. 일부 실시예들에서, 형성된 막들은 약 200보다 작거나, 약 100보다 작거나, 약 50보다 작거나, 약 30보다 작거나, 약 20보다 작거나, 또는 약 15 μΩcm보다 작은 비저항을 갖는다. 일반적으로 막이 더 얇을 때, 비저항은 벌크 막 또는 물질을 위하여 더 높을 수 있고, 예를 들어 5 nm보다 작은 두께를 갖는 막들이 약 200 μΩcm보다 작은 비저항을 나타낼 수 있는 한편, 동일한 퇴적 공정 및 조건들에 의한 더 두꺼운 막들은 약 20 μΩcm보다 작은 비저항을 나타낼 수 있다. 예를 들어, 본 발명의 실시예들은 텅스텐 전구체와, 수소를 포함하는 전구체, 예를 들어 수소 전구체와 같은 환원하는 반응물을 포함하는 전구체와의 반응과 연관될 수 있다. 이러한 실시예에서, 텅스텐 헥사플루오라이드(WF6)의 텅스텐 전구체는 수소의 여기된 종들 또는 원자 수소와 같은 수소 종들을 포함하는 수소 전구체와 다음의 반응으로 반응할 수 있다,
WF6 + 6H → W + 6 HF,
적어도 하나의 실시예에서, 수소는 원자 종일 수 있거나, 또는 핫 와이어에 노출될 때 여기되거나 화학적으로 활성화되는 종들이 될 수 있다.
[32] 본 발명의 실시예들은 집적 회로 제조 동안에 마이크로미터 스케일(또는 더 작은) 피쳐들 상에 금속을 선택적으로 퇴적하는 것에 관할 수 있다. 예를 들어, 여기 설명된 공정 플로우들은 100 마이크로미터보다 작거나, 1 마이크로미터보다 작거나, 또는 200 nm보다 작은 사이즈를 갖는 피쳐들을 제조하도록 사용될 수 있다. 상호접속부들을 위한 구리 상의 텅스텐의 선택적 퇴적의 경우에, 피쳐의 사이즈 또는 선폭은 1 마이크로미터보다 작거나, 200 nm보다 작거나, 100 nm보다 작거나, 또는 50 nm보다 작거나, 또는 30 nm보다 작거나, 또는 20 nm보다 작을 수 있다. 당업자들은 더 큰 피쳐들 또는 더 작은 피쳐들 상의 선택적 퇴적이 개시된 방법들을 사용하여 다른 맥락들에서 가능함을 인식할 수 있다.
[33] 도 1은 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다. 상기 방법은 금속 전구체 흐름 단계(100) 및 비금속 흐름 단계(200)를 포함하며, 이들 모두 퍼지 단계를 포함한다. 비금속 흐름 단계(200)는 비금속 전구체가 핫 와이어와 접촉하거나 또는 가까운 인접부 내에 위치하도록 일어날 수 있다. 이러한 단계들 각각은 제1 경로(300) 및 필요하다면 제2 경로(310)를 통해 반복될 수 있다. 전체 사이클은 필요하다면 제3 경로(320)를 통해 반복될 수 있다. 상기 단계들은 요구되는 두께의 텅스텐 막을 형성하기 위하여 반복될 수 있다.
[34] 상기 방법은 다음의 조건들에서 일어날 수 있다. 반응 챔버 내의 압력은 약 0.001 mbar 내지 약 1000 mbar, 약 0.01 mbar 내지 약 100 mbar, 또는 약 0.05 mbar 내지 약 20 mbar의 범위일 수 있다. 기판 온도는 약 0 내지 약 800℃, 약 20 내지 약 500℃, 약 50 내지 약 450℃, 약 100 내지 약 400℃, 약 150 내지 약 350℃, 또는 약 250 내지 약 300℃, 또는 약 275℃의 범위일 수 있다. 기판 온도는 기판 홀더의 히터에 의해 유지될 수 있다. 핫 와이어 온도는 약 1000℃ 이상, 약 1000 내지 약 2500℃, 약 1100 내지 약 2000℃, 약 1200 내지 약 1900℃, 또는 약 1700 내지 약 1800℃, 또는 약 1750℃의 범위일 수 있다.
[35] 추가적으로, 반응 챔버 내의 월은 핫 월 또는 콜드 월일 수 있다. 핫 월 반응기는 더 작은 부피의 반응기들에서 가능할 수 있으니, 또한 뱃치 퍼니스 반응기들과 같은 더 큰 부피의 반응기들을 위하여도 가능하다. 반면에, 콜드 월 반응기는 수십 리터 오더의 부피를 갖는 큰 부피의 반응기를 위하여 가능할 수 있으나, 콜드 월 반응기는 또한 작은 부피를 갖도록 설계된 샤워헤드 반응기와 같은 작은 부피의 반응기일 수 있고, 및/또는 가능하게는 반응 챔버의 상부 내에 냉각 시스템을 구비하는 반응기일 수 있다. 핫 월 반응기에서, 웨이퍼가 웨이퍼 홀더 및 웨이퍼 위에 놓여지는 커버 모두가 가열되는 챔버 내에 놓여질 수 있거나, 웨이퍼가 반응기 내에, 반응 챔버 부분들 및/또는 월들 모두가 기판의 온도와 동일하거나 가까운 반응기 내에 놓여질 수 있다. 핫 월에 대하여, 하나 또는 그 이상의 반응 챔버 월 및 기판의 온도 차이(양의 또는 음의)는 약 100℃보다 작을 수 있거나, 약 50℃보다 작을 수 있거나, 약 25℃보다 작을 수 있거나, 약 5℃보다 작을 수 있거나, 또는 약 0℃일 수 있고, 별개의 히터에 의해 유지될 수 있다. 콜드 월에 대하여, 하나 또는 그 이상의 반응 챔버 월(기판보다 더 차가운) 및 기판(챔버 월들보다 더 뜨거운)의 온도 차이는 약 25℃ 이상이거나, 약 50℃ 이상이거나, 약 75℃ 이상이거나, 또는 약 100℃ 이상일 수 있다.
[36] 도 2는 본 발명의 적어도 하나의 실시예에 따른 방법을 도시한다. 상기 방법은 도 1에서 표시된 것과 동일하며, 차이는 비금속 전구체 흐름 단계(200)가 금속 전구체 흐름 단계(100)에 선행하는 것이며, 이들 모두 퍼지 단계를 포함한다. 이러한 단계들 각각은 필요하다면 제1 경로(300) 및 제2 경로(310)를 통해 반복될 수 있다. 전체 사이클은 필요하다면 제3 경로(320)를 통해 반복될 수 있다. 상기 단계들은 요구되는 두께의 금속 막을 형성하기 위하여 반복될 수 있다. 금속 막은 전이 금속, 금속성 물질, 원소 전이 금속 막, 원소 텅스텐, 원소 몰리브덴 중 적어도 하나를 포함할 수 있다.
[37] 상기 방법은 다음의 조건들에서 일어날 수 있다. 반응 챔버 내의 압력은 약 0.001 mbar 내지 약 1000 mbar, 약 0.01 mbar 내지 약 100 mbar, 또는 약 0.05 mbar 내지 약 20 mbar, 또는 일부 예시들에서 약 0.05 mbar의 범위일 수 있다. 기판 온도는 약 0 내지 약 800℃, 약 20 내지 약 500℃, 약 50 내지 약 450℃, 약 100 내지 약 400℃, 약 150 내지 약 350℃, 또는 약 250 내지 약 300℃의 범위일 수 있고, 기판 홀더의 히터에 의해 유지될 수 있다. 핫 와이어 온도는 약 1000℃ 이상, 약 1000 내지 약 2500℃, 약 1100 내지 약 2000℃, 약 1200 내지 약 1900℃, 또는 약 1700 내지 약 1750℃의 범위일 수 있다.
[38] 도 3은 금속 전구체 흐름 단계(100)를 도시하며, 이는 금속 흐름(110) 및 임의적(optional) 비활성 가스 흐름(120)을 포함한다. 금속 흐름(110)은 금속 전구체의 흐름, 노출 또는 펄스와 연관된다. 금속 전구체는 전이 금속 원소; IV 족 원소; V 족 원소, VI 족 원소; 텅스텐-함유 전구체; 전이 금속 할라이드; 전이 금속 플루오라이드; 텅스텐 헥사플루오라이드(WF6); 또는 몰리브덴 플루오라이드(MoF5 또는 MoF6), 몰리브덴 클로라이드(MoCl5) 또는 다른 몰리브덴 할라이드들과 같은 몰리브덴-함유 전구체 중 적어도 하나를 포함할 수 있다. 흐름 단계(110) 내의 금속 전구체의 유속은 약 1 내지 약 1000 sccm, 약 3 내지 약 500 sccm, 또는 약 5 내지 약 250 sccm의 범위일 수 있다. 일부 실시예들에서, 흐름 단계(110) 내의 금속 전구체의 유속은 약 3 sccm일 수 있다. 금속 전구체 흐름 단계(110)의 기간은 0.01 내지 20초, 0.05 내지 10초, 또는 0.1 내지 5초의 범위일 수 있고, 또는 일부 예시들에서 약 0.5초일 수 있다. 다수의 기판들을 갖는 뱃치 반응기의 경우에, 예를 들어 시간은 더 길어질 수 있고 흐름들은 위에 언급한 것보다 더 높을 수 있다.
[39] 임의적 비활성 가스 흐름(120)은 퍼지 가스의 흐름을 포함할 수 있다. 퍼지 가스는 아르곤, 질소, 헬륨 또는 다른 희귀 또는 비활성 가스들 중 적어도 하나일 수 있다. 임의적 비활성 가스 흐름(120)의 유속은 약 25 내지 약 5000 sccm, 약 50 내지 약 2500 sccm, 또는 약 100 내지 약 2000 sccm의 범위일 수 있다. 임의적 비활성 가스 흐름 단계(120)의 기간은 약 0.1 내지 약 60초, 약 0.5 내지 약 20초, 또는 약 1 내지 약 10초의 범위일 수 있고, 또는 일부 예시들에서 약 7초일 수 있다. 본 발명의 적어도 하나의 실시예에서, 임의적 비활성 가스 흐름(120) 내에 비활성 가스의 흐름이 없을 수 있다. 일부 예시들에서, 예를 들어 다수의 기판들을 갖는 뱃치 반응기의 경우에, 시간은 더 길어질 수 있고 예를 들어 약 60초보다 클 수 있고, 흐름들은 위에 언급한 것보다 더 높을 수 있다.
[40] 도 4는 비금속 전구체 흐름 단계(200)를 도시하며, 이는 비금속 흐름(210) 및 임의적 비활성 가스 흐름(220)을 포함한다. 비금속 흐름(210)은 비금속 전구체의 흐름, 노출 또는 펄스와 연관된다. 비금속 흐름(210)은 비금속 전구체가 핫 와이어 가까이 존재하거나 또는 접촉하여 여기된, 래디칼 또는 원자 종들의 형성을 유발하도록 비금속 전구체를 흘리는 단계와 연관될 수 있다. 비금속 전구체는 이로부터 여기된, 래디칼 또는 원자 종들이 핫 와이어에 의해 생성되는 수소(H2)와 같은, 수소를 포함하는 종 중 적어도 하나를 포함할 수 있다. 비금속 흐름(210)의 유속은 약 1 내지 약 2000 sccm, 약 5 내지 약 1000 sccm, 또는 약 50 내지 약 500 sccm의 범위일 수 있고, 일부 예시들에서 약 50 sccm일 수 있다. 일부 실시예들에서, 비금속 흐름(210)의 기간은 약 0.1 내지 약 60초, 약 0.5 내지 약 20초, 또는 약 1 내지 약 10초의 범위일 수 있고, 또는 일부 예시들에서 약 7초일 수 있다. 일부 예시들에서, 예를 들어 다수의 기판들을 갖는 뱃치 반응기의 경우에, 시간은 더 길어질 수 있고 예를 들어 약 60초보다 클 수 있고, 흐름들은 위에 언급한 것보다 더 높을 수 있다.
[41] 임의적 비활성 가스 흐름(220)은 퍼지 가스의 흐름을 포함할 수 있다. 퍼지 가스는 아르곤, 질소, 헬륨 또는 다른 희귀 가스들 중 적어도 하나일 수 있다. 임의적 비활성 가스 흐름(220)의 유속은 약 25 내지 약 5000 sccm, 약 50 내지 약 2500 sccm, 또는 약 100 내지 약 2000 sccm의 범위일 수 있다. 임의적 비활성 가스 흐름 단계(220)의 기간은 약 0.1 내지 약 60초, 약 0.5 내지 약 20초, 또는 약 1 내지 약 10초의 범위일 수 있고, 또는 일부 예시들에서 약 7초일 수 있다. 본 발명의 적어도 하나의 실시예에서, 임의적 비활성 가스 흐름(220) 내에 비활성 가스의 흐름이 없을 수 있다. 일부 예시들에서, 예를 들어 다수의 기판들을 갖는 뱃치 반응기의 경우에, 시간은 더 길어질 수 있고 예를 들어 약 60초보다 클 수 있고, 흐름들은 위에 언급한 것보다 더 높을 수 있다.
[42] 본 발명의 적어도 하나의 실시예에서, 선택적 퇴적은 기판 상에서 일어날 수 있다. 기판은 제1 표면과 제2 표면을 포함할 수 있다. 제1 표면은 전이 금속; 그 아래 배치된 원소 금속 또는 금속성 도전성 막을 구비하는 산화된 금속; 원소 금속; 금속성 표면; 텅스텐; 구리; 또는 코발트 중 적어도 하나를 포함할 수 있다. 제2 표면은 실리콘; 실리콘 및 산소; Si-O 결합들; SiO2; 로우-k 물질; 실리콘 산화물; 실리콘 질화물; 실리콘 카바이드; 실리콘 산질화물; 실리콘 이산화물; 또는 이들의 혼합물들 중 적어도 하나를 포함할 수 있다. 선택적 퇴적은 제1 표면 상에만 퇴적된 막이 형성되도록 일어날 수 있다.
[43] 도 5a는 핫 와이어 원자층 퇴적(ALD)을 통한 텅스텐의 퇴적 이전의 상면도로부터의 구조물(400)을 도시한다. 구조물(400)은 기판(410) 및 적어도 하나의 채널(420)을 포함한다. 기판(410)은 실리콘 이산화물(SiO2), 실리콘(Si), 실리콘 저머늄(SiGe), 또는 다른 적합한 물질 중 적어도 하나를 포함할 수 있다. 적어도 하나의 채널(420)은 텅스텐(W) 또는 다른 금속 중 적어도 하나를 포함할 수 있다.
[44] 전술한 핫 와이어 ALD 공정은 퇴적된 텅스텐이 적어도 하나의 채널(420) 상에만 형성되도록 구조물(400)에 적용될 수 있다. 이는 도 5b에 도시되며, 여기서 핫 와이어 금속 막(430)이 적어도 하나의 채널(420) 상에만 형성되고 기판(410) 상에 형성되지 않을 수 있다. 핫 와이어 금속 막(430)은 텅스텐(W), 또는 다른 금속 중 적어도 하나를 포함할 수 있다.
[45] 도 6a는 본 발명의 적어도 하나의 실시예에 따른 구조물(500)의 측면도를 도시한다. 구조물(500)은 기판(510), 기판 텅스텐 삽입부(520), 핫 와이어 퇴적된 텅스텐 층(530), 및 글루층(540)을 포함한다. 글루층(540)은 핫 와이어 퇴적 공정에 임의의 연결을 갖지 않을 수 있고, 단면 분석을 수행하기 위한 능력을 가능하게 하기 위해서일 수 있다.
[46] 도 6b는 도 6a에 도시된 구조물(500)의 확대도를 도시한다. 핫 와이어 퇴적 공정은 핫 와이어 퇴적된 텅스텐 층(530)을 위하여 16.92 nm의 막 두께를 얻을 수 있다.
[47] 적어도 하나의 실시예에서, 온도는 선택적 퇴적을 용이하게 하도록 선택될 수 있다. 퇴적은 일반적으로 제1 표면 상에서 표면적 또는 부피당 퇴적된 물질의 양(예를 들어 at/cm2 또는 at/cm3)이 제2 표면 상에서 표면적 또는 부피당 퇴적된 물질의 양보다 클 때 선택적인 것으로 정의된다. 표면들 상에 퇴적된 물질의 양이 각각의 층의 두께들을 측정함에 의해 결정될 수 있다. 일부 경우들에서, 비연속적 막에 기인하여 두께 측정이 가능하지 않을 수 있다. 일부 경우들에서, 선택비는 표면적 또는 부피당 퇴적된 원자들을 측정함에 의해 결정될 수 있다.
[48] 전술한 바와 같이, 선택비는 제1 표면(A) 상에 형성된 물질 빼기 제2 표면(B) 상에 형성된 물질의 양의, 제1 표면(A) 상에 형성된 물질의 양에 대한 비율로서 표현될 수 있다(즉, 선택비는 [(제1 표면 상의 퇴적)-(제2 표면 상의 퇴적)]/(제1 표면 상의 퇴적) 또는 [(A-B)/A]에 의해 계산되는 퍼센트로서 주어질 수 있다). 바람직하게는, 선택비는 약 70% 이상, 약 80% 이상, 약 90% 이상, 약 95% 이상, 약 98% 이상, 약 99% 이상, 또는 약 100%일 수 있다. 일부 경우들에서, 80% 이상의 선택비는 특정한 어플리케이션들을 위하여 수용 가능할 수 있다. 일부 경우들에서, 50% 이상의 선택비는 특정한 어플리케이션들을 위하여 수용 가능할 수 있다. 일부 실시예들에서, 퇴적 온도는 선택비가 약 95% 이상이도록 선택될 수 있다. 일부 실시예들에서, 퇴적 온도는 약 100%의 선택비가 달성되도록 선택될 수 있다.
[49] 일부 실시예들에서, 선택적으로 퇴적되는 막의 두께는 약 100 nm보다 작거나, 약 50 nm보다 작거나, 약 25 nm보다 작거나, 또는 약 10 nm보다 작거나, 약 0.5 nm 내지 약 100 nm, 또는 약 1 nm 내지 약 50 nm의 범위일 수 있다. 그러나 일부 경우들에서, 요구되는 레벨의 선택비, 예를 들어 50% 이상, 더욱 바람직하게 80% 이상은 약 2.5 nm 이상, 약 5 nm 이상, 약 10 nm 이상, 약 25 nm 이상, 또는 약 50 nm 이상의 선택적으로 퇴적된 막의 두께들에 의해 달성된다.
[50] 일부 실시예들에서, 선택적으로 퇴적된 막은 약 5 Å/사이클보다 작거나, 약 2.5 Å/사이클보다 작거나, 약 1.5 Å/사이클보다 작거나, 또는 약 1.0 Å/사이클보다 작은 성장속도를 가질 수 있다. 다른 실시예들에서, 선택적으로 퇴적된 막은 약 0.01 내지 약 5 Å/사이클, 약 0.05 내지 약 2.5 Å/사이클, 또는 약 0.1 내지 약 2 Å/사이클, 또는 일부 예시들에서 약 0.5 내지 약 1.5 Å/사이클, 또는 약 1.1 Å/사이클의 성장 속도를 가질 수 있다. 일부 실시예들에서, 선택적으로 퇴적된 막은 제2 표면보다 제1 표면 상에 약 2배보다 크거나, 약 5배보다 크거나, 약 10배보다 크거나 또는 약 50배보다 더 큰 높은 퇴적 속도를 가질 수 있다. 일부 실시예들에서, 퇴적은 제2 표면 상에서 일어나나, 제2 표면 상에 퇴적된 두께는 막 퇴적 공정 동안에 일어나는 식각, 예를 들어 제1 표면 상에서보다 제2 표면 상에서 더욱 두드러질 수 있는 식각에 의해 감소될 수 있다. 일부 실시예들에서, 제2 표면 상의 퇴적이 일어날 수 있으나, 퇴적된 물질은 퇴적 공정 동안에 제2 표면으로부터 거의 완전히 또는 완전히 제거될 수 있다.
[51] 일부 실시예들에서, 기판의 하나 또는 그 이상의 표면들의 하나 또는 그 이상의 전처리 및/또는 패시베이션 공정들 또는 처리들이 금속을 포함하는 막을 선택적으로 퇴적하는 단계 이전에 수행될 수 있다. 도 7은 금속 전구체 흐름(100) 및 비금속 전구체 흐름(200) 이전에 일어나는 패시베이션 또는 전처리 단계(10)를 도시한다. 패시베이션 또는 전처리들은 선택비 및 요구되는 표면 상에서의 성장을 향상시킬 수 있고, 성장을 감소시키거나 차단하고 일부 예시들에서는 거의 완전히 차단할 수 있다. 본 발명에 따른 적어도 하나의 실시예에서, 텅스텐의 전-퇴적 단계가 에어에 노출된다. 이러한 경우에, 텅스텐은 적어도 부분적으로 산화된 텅스텐, 즉 원자 수소를 갖는 표면 상의 텅스텐 산화물 종들을 가질 수 있고, 이는 텅스텐의 산화된 종들을 금속성 또는 원소 텅스텐으로 환원시킬 수 있다. 이는 텅스텐의 선택적인 핫 와이어 원자층 퇴적을 가능하게 할 수 있다.
[52] 일부 실시예에서, 전체 공정 플로우는 예를 들어 단일 웨이퍼 모듈과 같은 단일 반응 챔버 내에서 수행될 수 있다. 그러나 다른 실시예들에서, 다양한 단계들이 둘 또는 그 이상의 반응 챔버들 내에서 수행될 수 있다. 일부 실시예에서, 제2의 다른 반응 챔버가 그 내부에 패시베이션층 형성하도록 또한 사용될 수 있다. 임의적인 어닐링 또는 열처리 단계가 필요하거나 요구된다면, 기판은 이후 열 어닐링 또는 처리(만약 사용된다면) 및 선택적 퇴적이 수행되는 제2 반응 챔버로 이동될 수 있다. 일부 실시예에서, 어닐링 또는 열처리 단계는 제2 반응 챔버 내에서 수행될 수 있고, 기판은 제1 반응 챔버로, 또는 선택적 퇴적이 수행되는 제3 반응 챔버로 다시 이동된다.
[53] 일부 실시예에서, 제1 표면 처리는 제1 반응 챔버 내에서 수행될 수 있고 선택적 퇴적은 제2의 다른 반응 챔버 내에서, 제1 표면 처리와 퇴적 단계 사이의 어닐링 단계 없이 수행될 수 있다. 기판은 만약 요구된다면 이동 이전에 일 기간의 시간 동안 냉각될 수 있다. 일부 실시예들에서, 냉각은 약 0 내지 30분, 또는 약 0 내지 10분 동안, 진공 내지 약 2 atm, 또는 약 0.1 torr 내지 약 760 torr, 또는 약 1 torr 내지 약 760 torr 범위의 압력에서 수행된다. 기판은 예를 들어 진공 하에서 또는 약 1 내지 1000 torr에서 N2의 존재(및 가능하게는 일부 O2) 내에서 이동될 수 있다.
[54] 본 발명의 적어도 하나의 실시예에서, 대략 15 μΩcm의 낮은 비저항의 텅스텐 막이 얻어질 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐 막은 약 100보다 작거나, 약 50보다 작거나, 약 30보다 작거나, 약 20보다 작거나, 또는 약 15 μΩcm보다 작은 비저항을 가질 수 있다. 낮은 비저항은 핫 월 반응기 내에서 더욱 얻어지기 쉬울 수 있는 한편, 더 높은 비저항은 콜드 월 반응기 내에서 얻어질 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐막은 X선 회절(XRD)에 의해 특징지어지는 알파-상(alpha-phase) 텅스텐을 포함할 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐 막은 알파-상 텅스텐을 약 50%보다 많이 포함할 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐 막은 알파-상 텅스텐 및 베타-상 텅스텐을 모두 포함할 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐 막은 전부 또는 거의 전부 알파-상 텅스텐일 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐의 퇴적은 선택적이지 않을 수 있다. 다른 실시예들에서, 낮은 비저항 텅스텐의 퇴적은 선택적이다. 일부 실시예들에서, 낮은 비저항 텅스텐의 퇴적은 기판의 표면 상에 존재하는 오직 하나의 물질만을 갖는 기판 상에 퇴적될 수 있다. 일부 실시예들에서, 낮은 비저항 텅스텐의 퇴적은 표면 상에 하나 이상의 물질이 존재하는 기판 상에 퇴적될 수 있다.
[55] 일부 실시예들에서, 텅스텐 막과 같은 전이 금속 막은 텅스텐과 같은 전이 금속을 약 75 at%보다 많거나, 약 85 at%보다 많거나, 약 90 at%보다 많거나, 약 95 at%보다 많거나, 약 98 at%보다 많거나, 약 99 at%보다 많거나, 또는 약 99.5%보다 많이 포함할 수 있다. 일부 실시예들에서, 텅스텐 막과 같은 전이 금속 막은 불순물들을, 전이 금속 이외의 다른 금속들의 형태로서, 수소, 또는 플루오르와 같은 할로겐들을 포함할 수 있다. 불순물들은 약 25 at%보다 작거나, 약 15 at%보다 작거나, 약 10 at%보다 작거나, 약 5 at%보다 작거나, 약 2 at%보다 작거나, 약 1 at%보다 작거나, 또는 약 0.5 at%보다 작게 포함할 수 있다.
[56] 본 발명의 적어도 하나의 실시예에 따르면, 금속 또는 텅스텐 막의 선택적 퇴적은 반응기에 추가적인 종들을 첨가함에 의해 억제되거나 정지될 수 있다. 예를 들어, 텅스텐의 선택적 퇴적은 반응기에 N2O 또는 NH3와 같은 질화 종들을 첨가함에 의해 완전히 정지될 수 있다. 다른 예시에서, O2와 같은 산화 종들의 첨가는 퇴적을 억제하지만 완전히 정지시키지는 않으나, 수소 래디칼들 또는 원자 수소와 같은 수소의 여기된 종들에 의한 적절한 처리는 퇴적이 진행되는 것을 가능하게 할 수 있다.
[57] 도 8은 본 발명의 적어도 하나의 실시예에 따른 공정을 도시한다. 상기 공정은 코발트와 같은 다른 금속층을 포함하거나 구비하는 기판의 제1 표면 상에, 실리콘 이산화물층과 같은 기판의 제2 표면에 대하여, 텅스텐과 같은 금속을 선택적으로 퇴적하는 것에 관한 것이다. 상기 공정은 임의적인 금속 산화물 제거/변환(600) 및 금속 퇴적(700)을 포함할 수 있다. 공정 단계들은 반복될 수 있고, 단계들의 순서는 필요한 대로 변환될 수 있다. 적어도 하나의 실시예에 따르면, 임의적 금속 산화물 제거/변환(600)은, 금속 퇴적(700)의 초기 50 사이클 이전 또는 동안에; 금속 퇴적(700)의 초기 20 사이클들 이전에 또는 도중에; 또는 금속 퇴적(700)의 초기 10 사이클 이전 또는 동안과 같이, 금속 퇴적(700) 이전에 또는 도중에 일어날 수 있다.
[58] 임의적 금속 산화물 제거/변환(600)은 금속 산화물을 부분적으로 또는 전부 제거할 수 있다. 임의적 금속 산화물 제거/변환(600)은 금속 산화물의 여분의 양을 제거하거나 금속 산화물을 금속 막으로 변환시킬 수 있다. 임의적 금속 산화물 제거/변환(600) 내에서 제거된 금속 산화물은 텅스텐 산화물 또는 코발트 산화물을 포함할 수 있다.
[59] 본 발명의 적어도 하나의 실시예에 따르면, 임의적 금속 산화물 제거/변환(600)은 반응기 내에서 기판에 도달하기 전에 핫 와이어를 접촉하는 수소를 흘리는 단계를 포함할 수 있다. 수소의 핫 와이어와의 접촉은 H2의 원자 H로의 분해(breakup)를 유발한다. 반응기는 100 내지 400℃, 200 내지 350℃, 또는 250 내지 300℃ 범위의 온도에서 설정될 수 있다. 반응기 내의 압력은 0.01 mbar보다 높거나, 0.05 mbar보다 높거나, 또는 0.2 mbar보다 높을 수 있다. 수소 흐름은 25 sccm보다 크거나, 50 sccm보다 크거나, 또는 75 sccm보다 클 수 있다. 핫 와이어 온도는 약 1000℃ 이상, 약 1000 내지 약 2500℃, 약 1100 내지 약 2000℃, 약 1200 내지 약 1900℃, 또는 약 1700 내지 약 1750℃ 범위일 수 있다. 임의적 금속 산화물 제거/변환(600)은 1 내지 30분, 2 내지 20분, 또는 5 내지 15분 동안 지속될 수 있다.
[60] 임의적 금속 산화물 제거/변환(600)은 금속층을 남기며 금속 산화물의 제거를 유발할 수 있다. 이러한 코발트층의 상면 상에 금속 퇴적(700)은 텅스텐 층을 퇴적할 수 있다. 도 9는 본 발명의 적어도 하나의 실시예에 따른 금속 퇴적(700)을 도시한다. 금속 퇴적(700)은 수소 펄스/퍼지(710) 및 금속 전구체 펄스/퍼지(720)를 포함할 수 있다. 기판 홀더 히터에 의해 유지될 수 있는 기판 온도는, 약 0 내지 약 800℃, 약 20 내지 약 500℃, 약 50 내지 약 450℃, 약 100 내지 400℃, 약 150 내지 약 350℃, 또는 약 250 내지 약 300℃, 또는 약 275℃의 범위일 수 있다. 반응기 내의 압력은 0.01 mbar보다 크거나, 0.05 mbar보다 크거나, 또는 0.2 mbar보다 클 수 있다. 공정 단계들은 반복될 수 있고, 단계들의 순서는 필요한 대로 변환될 수 있다.
[61] 수소 펄스/퍼지(710)는 1 내지 5000 sccm, 5 내지 2000 sccm, 10 내지 1000 sccm, 20 내지 800 sccm, 또는 일부 경우들에서, 20 내지 80 sccm 또는 40 내지 60 sccm 범위의 속도로 수소를 우선 흘리는 단계를 포함할 수 있다. 수소 흐름은 0.1 내지 60초, 0.5 내지 60초, 1 내지 30초, 4 내지 15초, 또는 7 내지 10초 범위의 기간 동안 일어날 수 있다. 수소 펄스/퍼지(710)는 또한 임의의 여분의 수소를 제거하도록 퍼지 가스를 흘리는 단계를 포함할 수 있다. 퍼지 가스는 예를 들어 질소 또는 아르곤을 포함할 수 있다. 퍼지 가스 흐름은 0.1 내지 60초, 1 내지 20초, 4 내지 15초, 또는 7 내지 10초 범위의 기간 동안 일어날 수 있다. 일부 실시예들에서, 퍼지(710)가 필요하지 않거나 1.0초보다 작을 수 있다.
[62] 금속 전구체 펄스/퍼지(720)는 0.1 내지 15 sccm, 1 내지 10 sccm, 또는 3 내지 7 sccm 범위의 속도로 금속 전구체를 우선 흘리는 단계를 포함할 수 있다. 금속 전구체는 전이 금속 원소; IV 족 원소; V 족 원소, VI 족 원소; 텅스텐-함유 전구체; 전이 금속 할라이드; 전이 금속 플루오라이드; 텅스텐 헥사플루오라이드(WF6); 또는 MoF5 또는 MoF6와 같은 몰리브덴 플루오라이드와 같은 몰리브덴-함유 전구체 중 적어도 하나를 포함할 수 있다. 금속 전구체 흐름은 0.1 내지 10초, 0.2 내지 5초, 또는 0.5 내지 3초 범위의 기간 동안 일어날 수 있다. 금속 펄스/퍼지(720)는 또한 임의의 여분의 금속 전구체를 제거하도록 퍼지 가스를 흘리는 단계를 포함할 수 있다. 퍼지 가스는 예를 들어 질소 또는 아르곤을 포함할 수 있다. 퍼지 가스는 0.1 내지 60초, 1 내지 20초, 4 내지 15초, 또는 7 내지 10초 범위의 기간 동안 일어날 수 있다. 일부 실시예들에서, 퍼지(720)가 요구되지 않거나, 1.0초보다 작을 수 있다.
[63] 도 10은 본 발명의 적어도 하나의 실시예에 따라 형성된 소자(800)를 도시한다. 소자(800)는 텅스텐층(810)(검은 층으로 표시됨), 코발트층(820)(어두운 회색층으로 표시됨), 및 실리콘 이산화물층(830)(밝은 회색층으로 표시됨)을 포함할 수 있다. 핫 와이어의 사용이 실리콘 이산화물층(830)의 노출된 부분들 상이 아닌, 코발트층(820) 상에 텅스텐층(810)이 선택적으로 퇴적되는 것을 가능하게 한다. 추가적으로, 티타늄 접착층(도시되지 않음)이 실리콘 이산화물층(830)과 코발트층(820) 사이에 배치될 수 있다.
[64] 도 11은 본 발명의 적어도 하나의 실시예에 따라 형성된 반도체 구조물(900)을 도시한다. 반도체 구조물(900)은 40의 종횡비(피쳐 깊이:폭)을 갖는 3차원 구조물 상의 핫 와이어 텅스텐 공정의 결과로서 우수한 콘포말리티를 나타낸다. 텅스텐 막은 3차원 구조물 상에서 콘포말하다.
[65] 도 11에 도시된 샘플들의 준비에서, 알루미늄 산화물층(920)이 구조물들(930) 상에 형성되었고, 0.5 nm의 비정질 실리콘 시드층이 뒤따랐다. 여기 설명된 핫 와이어 퇴적 방법들을 사용하여 12 nm의 W(910)의 퇴적이 뒤따랐다. 이후, 샘플들은 비정질 실리콘의 두꺼운 층으로 캡핑되었다. 일부 실시예들에서, 핫 와이어 퇴적된 금속막(선택적 또는 비선택적 금속막, 예를 들어 텅스텐 막과 같은)은 약 2보다 크거나, 약 5보다 크거나, 약 10보다 크거나, 약 20보다 크거나, 일부 경우들에서 약 40보다 크거나 또는 약 80보다 큰 종횡비들(깊이:폭)에서, 약 50%보다 크거나, 약 80%보다 크거나, 약 90%보다 크거나, 약 95%보다 크거나, 약 98%보다 크거나, 약 99%보다 큰 스텝 커버리지(step coverage)를 갖는다. 트렌치들 또는 비아들보다 더욱 복잡한 구조물들에 대하여 종횡비를 결정하기 어렵지만, 이러한 맥락에서는 종횡비가 웨이퍼/기판 또는 웨이퍼/기판의 부분의 평평한 표면적에 대한, 웨이퍼/기판 또는 웨이퍼/기판의 부분 내의 구조물들의 총 표면적의 비율인 것으로 이해될 수 있다는 점에 주목할 수 있다.
[66] 예시들
[67] 아래의 예시들은 본 개시의 예시적인 실시예들의 다양한 태양들을 도시한다. 여기 반영되는 조성들, 방법들 및 다양한 변수들은 본 개시의 다양한 태양들 및 실시예들을 예시화하기 위한 것으로 의도될 뿐이며, 청구된 발명의 범위를 제한하도록 의도되지는 않는다.
1. 금속막을 형성하기 위한 방법으로서,
반응 챔버 내에 공정을 위한 기판과, 상기 반응 챔버를 통하여 적어도 하나의 가스를 통과시키기 위한 핫 와이어를 제공하되, 상기 기판 표면은 코발트를 포함하는, 상기 제공 단계;
상기 기판 상으로 상기 핫 와이어와 접촉되는 수소 전구체를 흘리는 단계;
상기 기판 상으로 금속 전구체를 흘리는 단계; 및
코발트를 포함하는 상기 표면 상에 상기 금속 전구체와, 상기 핫 와이어와 접촉된 상기 수소 전구체 사이의 반응에 의해 금속 또는 금속성 막을 선택적으로 형성하는 단계를 포함하는 방법.
2. 예시 1의 방법에 있어서, 상기 금속 전구체는, 전이 금속 원소; IV 족 원소; V 족 원소, VI 족 원소; 텅스텐-함유 전구체; 전이 금속 할라이드; 전이 금속 플루오라이드; 텅스텐 헥사플루오라이드(WF6); 또는 MoF5 또는 MoF6와 같은 몰리브덴 플루오라이드와 같은 몰리브덴-함유 전구체 중 적어도 하나를 포함하는 방법.
3. 예시 1-2 중 어느 하나의 방법에 있어서, 상기 수소 전구체는 수소(H2) 중 적어도 하나를 포함하는 방법.
4. 예시 1-3 중 어느 하나의 방법에 있어서, 상기 표면은 코발트 산화물을 포함하고, 상기 기판 상으로 수소 전구체를 흘리는 단계는 코발트 산화물을 부분적으로 환원시키는 방법.
5. 예시 4의 방법에 있어서, 상기 수소 전구체는 상기 핫 와이어를 접촉하는 방법.
6. 예시 1-5 중 어느 하나의 방법에 있어서, 형성된 상기 금속막은 텅스텐을 포함하는 방법.
7. 예시 1-6 중 어느 하나의 방법에 있어서, 상기 금속막을 선택적으로 형성하는 단계는 ALD 공정을 포함하는 방법.
8. 예시 1-7 중 어느 하나의 방법에 있어서, 상기 금속막을 선택적으로 형성하는 단계는 사이클 공정을 포함하는 방법.
9. 예시 1-8 중 어느 하나의 방법에 있어서, 상기 금속막을 선택적으로 형성하는 단계는 사이클 또는 순차적 CVD 공정을 포함하는 방법.
10. 예시 1-9 중 어느 하나의 방법을 수행하도록 구성된 반응 챔버.
11. 예시 1-10 중 어느 하나의 방법에 있어서, 상기 기판 표면은 코발트 산화물을 포함하는 방법.
12. 예시 11의 방법에 있어서, 상기 코발트 산화물은 금속성 코발트로 적어도 환원되고 부분적으로 환원되는 방법.
13. 예시 1-12 중 어느 하나의 방법에 있어서, 상기 기판은 또한 SiO2를 포함하는 다른 표면을 포함하는 방법.
14. 예시 13의 방법에 있어서, 상기 금속 또는 금속성 막은 SiO2를 포함하는 다른 기판에 대하여 코발트를 포함하는 상기 표면 상에 선택적으로 퇴적되는 방법.
15. 예시 1-14 중 어느 하나의 방법에 있어서, 상기 반응 챔버는 핫-월 반응 챔버인 방법.
16. 금속막을 형성하기 위한 방법으로서,
반응 챔버 내에 공정을 위한 기판과, 상기 반응 챔버를 통하여 적어도 하나의 가스를 통과시키기 위한 핫 와이어를 제공하되, 상기 기판 표면은 코발트를 포함하는, 상기 제공 단계;
상기 기판을 상기 핫 와이어와 접촉된 수소 전구체에 노출하는 단계;
상기 기판을 금속 전구체에 노출하는 단계; 및
코발트를 포함하는 상기 표면 상에 상기 금속 전구체와, 상기 핫 와이어와 접촉된 상기 수소 전구체 사이의 반응에 의해 금속 또는 금속성 막을 선택적으로 형성하는 단계를 포함하는 방법.
17. 예시 16의 방법에 있어서, 상기 금속 전구체는, 전이 금속 원소; IV 족 원소; V 족 원소, VI 족 원소; 텅스텐-함유 전구체; 전이 금속 할라이드; 전이 금속 플루오라이드; 텅스텐 헥사플루오라이드(WF6); 또는 MoF5 또는 MoF6와 같은 몰리브덴 플루오라이드와 같은 몰리브덴-함유 전구체 중 적어도 하나를 포함하는 방법.
18. 예시 16-17 중 어느 하나의 방법에 있어서, 상기 수소 전구체는 수소(H2) 중 적어도 하나를 포함하는 방법.
19. 예시 16-18 중 어느 하나의 방법에 있어서, 상기 표면은 코발트 산화물을 포함하고, 상기 기판 상으로 수소 전구체를 흘리는 단계는 코발트 산화물을 부분적으로 환원시키는 방법.
20. 예시 19의 방법에 있어서, 상기 수소 전구체는 상기 핫 와이어와 접촉하는 방법.
21. 예시 16-20 중 어느 하나의 방법에 있어서, 형성된 상기 금속막은 텅스텐을 포함하는 방법.
22. 예시 16-21 중 어느 하나의 방법에 있어서, 상기 금속막을 선택적으로 형성하는 단계는 ALD 공정을 포함하는 방법.
23. 예시 16-22 중 어느 하나의 방법에 있어서, 상기 금속막을 선택적으로 형성하는 단계는 사이클 공정을 포함하는 방법.
24. 예시 16-23 중 어느 하나의 방법에 있어서, 상기 금속막을 선택적으로 형성하는 단계는 사이클 또는 순차적 CVD 공정을 포함하는 방법.
25. 예시 16-24 중 어느 하나의 방법을 수행하도록 구성된 반응 챔버.
26. 예시 16의 방법에 있어서, 상기 기판 표면은 코발트 산화물을 포함하는 방법.
27. 예시 26의 방법에 있어서, 상기 코발트 산화물은 금속성 코발트로 적어도 환원되고 부분적으로 환원되는 방법.
28. 예시 16-27 중 어느 하나의 방법에 있어서, 상기 기판은 또한 SiO2를 포함하는 다른 표면을 포함하는 방법.
29. 예시 16-28 중 어느 하나의 방법에 있어서, 상기 금속 또는 금속성 막은 SiO2를 포함하는 다른 기판에 대하여 코발트를 포함하는 상기 표면 상에 선택적으로 퇴적되는 방법.
30. 예시 16-29 중 어느 하나의 방법에 있어서, 상기 반응 챔버는 핫-월 반응 챔버인 방법.
31. 금속막을 형성하기 위한 방법으로서,
반응 챔버 내에 공정을 위한 3차원 구조물을 구비하는 기판과, 상기 반응 챔버를 통하여 적어도 하나의 가스를 통과시키기 위한 핫 와이어를 제공하는 단계;
상기 기판 상으로 상기 핫 와이어와 접촉된 수소 전구체를 흘리는 단계;
상기 기판 상으로 금속 전구체를 흘리는 단계; 및
상기 3차원 구조물 상에 상기 금속 전구체와, 상기 핫 와이어와 접촉된 상기 수소 전구체 사이의 반응에 의해 금속 또는 금속성 막을 형성하는 단계를 포함하고,
금속 또는 금속성 막은 약 5보다 큰 종횡비를 갖는 상기 3차원 구조물 내에서 약 50%보다 큰 스텝 커버리지를 갖는 방법.
32. 예시 31의 방법에 있어서, 상기 금속 또는 금속성 막은 약 5보다 큰 종횡비를 갖는 상기 3차원 구조물 내에서 약 80%보다 큰 스텝 커버리지를 갖는 방법.
33. 예시 31-32 중 어느 하나의 방법에 있어서, 상기 금속 또는 금속성 막은 약 20보다 큰 종횡비를 갖는 상기 3차원 구조물 내에서 약 50%보다 큰 스텝 커버리지를 갖는 방법.
34. 예시 31-33 중 어느 하나의 방법에 있어서, 상기 금속 또는 금속성 막은 전이 금속 막을 포함하는 방법.
35. 예시 31-34 중 어느 하나의 방법에 있어서, 상기 금속 또는 금속성 막은 텅스텐 막인 방법.
36. 예시 31-35 중 어느 하나의 방법에 있어서, 상기 반응 챔버는 핫-월 반응 챔버의 일부분인 방법.
37. 예시 31-36 중 어느 하나의 방법을 수행하도록 구성된 반응 챔버.
38. 텅스텐막을 선택적으로 형성하기 위한 방법으로서,
반응 챔버 내에 공정을 위한 제1 표면과 제2 표면을 포함하는 기판과, 가스의 여기된 종들을 생성하기 위한 핫 와이어를 제공하는 단계;
상기 기판 상으로 텅스텐 전구체 펄스/퍼지 단계를 수행하는 단계로서,
상기 기판 상으로 텅스텐 전구체를 펄스하는 단계; 및
상기 반응 챔버로부터 여분의 상기 텅스텐 전구체를 퍼지하는 단계를 포함하는, 텅스텐 전구체 펄스/퍼지 단계를 수행하는 단계; 및
상기 기판 상으로 수소 전구체 펄스/퍼지 단계를 수행하는 단계로서,
상기 기판 상으로 상기 핫 와이어에 의해 여기된 수소 전구체를 펄스하는 단계; 및
상기 반응 챔버로부터 여분의 상기 수소 전구체를 퍼지하는 단계를 포함하는, 수소 전구체 펄스/퍼지 단계를 수행하는 단계를 포함하고,
상기 텅스텐 전구체는 텅스텐 헥사플루오라이드(WF6) 중 적어도 하나를 포함하고,
상기 수소 전구체는 수소(H2) 중 적어도 하나를 포함하고,
상기 핫 와이어의 온도는 약 1000℃ 이상이고,
텅스텐 막은 상기 제1 표면 상에 선택적으로 형성되는 방법.
39. 예시 38의 방법에 있어서, 상기 반응 챔버 내의 벽은 핫 월인 방법.
40. 예시 39의 방법에 있어서, 상기 핫 월과 상기 기판의 온도 차이는 100℃일 수 있거나, 약 50℃보다 작을 수 있거나, 약 25℃보다 작을 수 있거나, 약 5℃보다 작을 수 있거나, 또는 약 0℃일 수 있는 방법.
41. 예시 38의 방법에 있어서, 상기 반응 챔버 내의 벽은 콜드 월인 방법.
42. 예시 41의 방법에 있어서, 상기 콜드 월과 상기 기판의 온도 차이는 약 100℃보다 작을 수 있거나, 약 50℃보다 작을 수 있거나, 약 25℃보다 작을 수 있거나, 약 5℃보다 작을 수 있거나, 또는 약 0℃일 수 있는 방법.
43. 예시 38-42 중 어느 하나의 방법에 있어서, 상기 반응 챔버의 압력은 약 0.001 mbar 내지 약 1000 mbar, 약 0.01 mbar 내지 약 100 mbar, 또는 약 0.05 mbar 내지 약 20 mbar의 범위인 방법.
44. 예시 38-43 중 어느 하나의 방법에 있어서, 상기 여분의 텅스텐 전구체를 퍼지하는 단계는 상기 반응 챔버를 질소(N2), 아르곤(Ar), 헬륨(He), 또는 다른 희귀 또는 비활성 가스들 중 적어도 하나로 퍼지하는 단계를 포함하는 방법.
45. 예시 38-42 중 어느 하나의 방법에 있어서, 상기 여분의 수소 전구체를 퍼지하는 단계는 상기 반응 챔버를 질소(N2), 아르곤(Ar), 헬륨(He), 또는 다른 희귀 또는 비활성 가스들 중 적어도 하나로 퍼지하는 단계를 포함하는 방법.
46. 금속을 포함하는 막을 선택적으로 형성하기 위한 방법으로서,
반응 챔버 내에 공정을 위한 기판과, 적어도 하나의 가스와 접촉하기 위한 핫 와이어 성분을 제공하는 단계;
상기 기판을 금속 전구체에 노출하는 단계; 및
상기 기판을 상기 핫 와이어의 인접부에 노출되었던 가스에 노출하는 단계를 포함하고,
상기 기판은 적어도 두 개의 다른 물질들을 포함하고, 상기 금속 막은 상기 표면들 중 하나 내에 선택적으로 형성되는 방법.
47. 예시 46의 방법에 있어서, 상기 금속 전구체는 전이 금속 원소를 포함하는 방법.
48. 예시 46의 방법에 있어서, 상기 금속 전구체는 IV 족, V 족, 또는 VI 족 원소를 포함하는 방법.
49. 예시 46의 방법에 있어서, 상기 금속 전구체는 텅스텐-함유 전구체 또는 몰리브덴-함유 전구체를 포함하는 방법.
50. 예시 46-49 중 어느 하나의 방법에 있어서, 상기 가스는 환원 가스를 포함하는 방법.
51. 예시 46-50 중 어느 하나의 방법에 있어서, 상기 가스는 수소를 포함하는 방법.
52. 예시 46의 방법에 있어서, 상기 선택적으로 형성된 막은 전이 금속을 포함하는 방법.
53. 예시 46-52 중 어느 하나의 방법에 있어서, 상기 선택적으로 형성된 막은 금속성 물질을 포함하는 방법.
54. 예시 46-53 중 어느 하나의 방법에 있어서, 상기 선택적으로 형성된 막은 원소 전이 금속 막을 포함하는 방법.
55. 예시 46-54 중 어느 하나의 방법에 있어서, 상기 선택적으로 형성된 막은 원소 텅스텐 또는 원소 몰리브덴을 포함하는 방법.
56. 예시 46-55 중 어느 하나의 방법에 있어서, 여기된 래디칼 또는 원자 종들은 상기 가스가 상기 핫 와이어의 인접부에 노출되었을 때 상기 가스로부터 형성되는 방법.
57. 예시 46-56 중 어느 하나의 방법에 있어서, 수소를 포함하는 여기된 래디칼 또는 원자 종들은 상기 가스가 상기 핫 와이어의 인접부에 노출되었을 때 상기 가스로부터 형성되는 방법.
58. 예시 46-57 중 어느 하나의 방법에 있어서, 상기 기판은 제1 표면 및 제2 표면을 포함하는 방법.
59. 예시 58의 방법에 있어서, 상기 제1 표면은 전이 금속을 포함하는 방법.
60. 예시 58-59 중 어느 하나의 방법에 있어서, 상기 제1 표면은 산화된 금속을 포함하고, 상기 산화된 금속 아래에 원소 금속 또는 금속성 도전성 막이 위치하는 방법.
61. 예시 58의 방법에 있어서, 상기 제2 표면은 실리콘을 포함하는 방법.
62. 예시 58의 방법에 있어서, 상기 제2 표면은 실리콘 및 산소를 포함하는 방법.
63. 예시 62의 방법에 있어서, 상기 제2 표면은 Si-O 결합들을 포함하는 방법.
64. 예시 58의 방법에 있어서, 상기 제2 표면은 SiO2 결합들을 포함하는 방법.
65. 예시 58의 방법에 있어서, 상기 제2 표면은 로우-k 물질을 포함하는 방법.
66. 예시 58의 방법에 있어서, 상기 제2 표면은 실리콘 산화물, 실리콘 질화물, 실리콘 카바이드, 실리콘 산질화물, 실리콘 이산화물, 또는 이들의 혼합물들을 포함하는 방법.
67. 예시 58의 방법에 있어서, 상기 제1 표면은 금속을 포함하고 상기 제2 표면은 실리콘 및 산소를 포함하는 방법.
68. 예시 58의 방법에 있어서, 상기 제1 표면은 원소 금속을 포함하고 상기 제2 표면은 실리콘 및 산소를 포함하는 방법.
69. 예시 58의 방법에 있어서, 상기 제1 표면은 금속성 표면을 포함하고 상기 제2 표면은 실리콘 및 산소를 포함하는 방법.
70. 예시 58의 방법에 있어서, 상기 제1 표면은 W, Cu, 또는 Co을 포함하고 상기 제2 표면은 실리콘 및 산소를 포함하는 방법.
71. 예시 58-70 중 어느 하나의 방법에 있어서, 상기 막은 상기 제1 표면 상에 선택적으로 형성되는 방법.
72. 예시 46-71 중 어느 하나의 방법에 있어서, 상기 기판을 상기 금속 전구체에 노출시키는 단계 이후에 상기 기판을 퍼지 가스에 노출시키는 단계를 더 포함하는 방법.
73. 예시 46-72 중 어느 하나의 방법에 있어서, 상기 기판을 상기 핫 와이어를 통해 통과한 상기 가스에 노출시키는 단계 이후에 상기 기판을 퍼지 가스에 노출시키는 단계를 더 포함하는 방법.
74. 예시 46-73 중 어느 하나의 방법에 있어서, 상기 핫 와이어 온도는 500℃ 이상인 방법.
75. 예시 46-74 중 어느 하나의 방법에 있어서, 상기 핫 와이어 온도는 1000℃ 이상인 방법.
76. 예시 46-75 중 어느 하나의 방법에 있어서, 상기 핫 와이어 온도는 1500℃ 이상인 방법.
77. 예시 46-76 중 어느 하나의 방법에 있어서, 선택비는 50% 이상인 방법.
78. 예시 46-77 중 어느 하나의 방법에 있어서, 선택비는 90% 이상인 방법.
79. 예시 46의 방법에 있어서, 상기 반응 챔버의 온도는 약 0℃ 내지 약 800℃로 유지되는 방법.
80. 예시 46-79 중 어느 하나의 방법에 있어서, 상기 막의 두께는 1 nm 이상인 방법.
81. 예시 46-80 중 어느 하나의 방법에 있어서, 상기 막의 두께는 5 nm 이상인 방법.
82. 예시 46-81 중 어느 하나의 방법에 있어서, 상기 막의 두께는 10 nm 이상인 방법.
83. 예시 46-82 중 어느 하나의 방법에 있어서, 상기 막의 두께는 25 nm 이상인 방법.
84. 예시 46의 방법에 있어서, 상기 반응 챔버의 벽은 핫 월인 방법.
85. 예시 84의 방법에 있어서, 상기 핫 월과 상기 기판의 온도 차이는 100℃일 수 있거나, 약 50℃보다 작을 수 있거나, 약 25℃보다 작을 수 있거나, 약 5℃보다 작을 수 있거나, 또는 약 0℃일 수 있는 방법.
86. 예시 46의 방법에 있어서, 상기 반응 챔버 내의 벽은 콜드 월인 방법.
87. 예시 86의 방법에 있어서, 상기 콜드 월과 상기 기판의 온도 차이는 약 100℃보다 작을 수 있거나, 약 50℃보다 작을 수 있거나, 약 25℃보다 작을 수 있거나, 약 5℃보다 작을 수 있거나, 또는 약 0℃일 수 있는 방법.
88. 예시 46-87 중 어느 하나의 방법에 있어서, 상기 반응 챔버 내의 압력은 약 0.001 mbar 내지 약 1000 mbar, 약 0.01 mbar 내지 약 100 mbar, 또는 약 0.05 mbar 내지 약 20 mbar의 범위인 방법.
89. 예시 46-88 중 어느 하나의 방법에 있어서, 상기 여분의 텅스텐 전구체를 퍼지하는 단계는 상기 반응 챔버를 질소(N2), 아르곤(Ar), 헬륨(He), 또는 다른 희귀 또는 비활성 가스들 중 적어도 하나로 퍼지하는 단계를 포함하는 방법.
90. 예시 46-89 중 어느 하나의 방법에 있어서, 상기 여분의 수소 전구체를 퍼지하는 단계는 상기 반응 챔버를 질소(N2), 아르곤(Ar), 헬륨(He), 또는 다른 희귀 또는 비활성 가스들 중 적어도 하나로 퍼지하는 단계를 포함하는 방법.
91. 예시 46-90 중 어느 하나의 방법에 있어서, 상기 막을 선택적으로 형성하는 단계는 ALD 공정을 포함하는 방법.
92. 예시 46-91 중 어느 하나의 방법에 있어서, 상기 막을 선택적으로 형성하는 단계는 사이클 공정을 포함하는 방법.
93. 예시 46-92 중 어느 하나의 방법에 있어서, 상기 막을 선택적으로 형성하는 단계는 사이클 또는 순차적 CVD 공정을 포함하는 방법.
94. 예시 46-93 중 어느 하나의 방법을 수행하도록 구성된 반응 챔버.
95. 텅스텐막을 형성하기 위한 방법으로서,
반응 챔버 내에 공정을 위한 기판과, 상기 반응 챔버를 통하여 적어도 하나의 가스를 통과시키기 위한 핫 와이어를 제공하는 단계;
상기 기판 상으로 텅스텐 전구체를 흘리는 단계; 및
상기 기판 상으로 상기 핫 와이어와 접촉된 수소 전구체를 흘리는 단계;를 포함하고,
상기 텅스텐 전구체와 상기 핫 와이어와 접촉된 상기 수소 전구체 사이의 반응이 텅스텐막을 형성하며, 상기 반응 챔버는 핫-월 반응 챔버인 방법.
96. 예시 95의 방법에 있어서, 상기 텅스텐 전구체는 텅스텐 헥사플루오라이드(WF6) 중 적어도 하나를 포함하는 방법.
97. 예시 95-96 중 어느 하나의 방법에 있어서, 상기 수소 전구체는 수소(H2) 중 적어도 하나를 포함하는 방법.
98. 예시 95-97 중 어느 하나의 방법에 있어서, 상기 핫 와이어의 온도는 약 1000℃, 약 1000 내지 약 2500℃, 약 1100 내지 약 2000℃, 약 1200 내지 약 1900℃, 또는 약 1700 내지 약 1750℃ 범위인 방법.
99. 예시 95-98 중 어느 하나의 방법에 있어서, 상기 반응 챔버로부터 여분의 상기 텅스텐 전구체를 퍼지하는 단계를 더 포함하는 방법.
100. 예시 95-99 중 어느 하나의 방법에 있어서, 상기 반응 챔버로부터 여분의 상기 수소 전구체를 퍼지하는 단계를 더 포함하는 방법.
101. 예시 95-100 중 어느 하나의 방법에 있어서, 상기 형성된 텅스텐 막은 약 100 μΩcm보다 작은 비저항을 갖는 방법.
102. 예시 95-101 중 어느 하나의 방법에 있어서, 상기 형성된 텅스텐 막은 약 50 μΩcm보다 작은 비저항을 갖는 방법.
103. 예시 95-102 중 어느 하나의 방법에 있어서, 상기 형성된 텅스텐 막은 약 15 μΩcm보다 작은 비저항을 갖는 방법.
104. 예시 95-103 중 어느 하나의 방법에 있어서, 상기 텅스텐 막을 형성하는 단계는 ALD 공정을 포함하는 방법.
105. 예시 95-104 중 어느 하나의 방법에 있어서, 상기 텅스텐 막을 형성하는 단계는 사이클 공정을 포함하는 방법.
106. 예시 95-105 중 어느 하나의 방법에 있어서, 상기 텅스텐 막을 형성하는 단계는 사이클 또는 순차적 CVD 공정을 포함하는 방법.
107. 예시 95-106 중 어느 하나의 방법을 수행하도록 구성된 반응 챔버.
[68] 도시되고 설명되는 특정한 실행예들은 본 발명 및 그 최적의 방식을 도시하며, 임의의 방식으로 태양들 및 실행예들의 범위를 다르게 제한하도록 의도되지 않는다. 실제로, 간략화를 위하여, 통상의 제조, 연결, 준비, 및 시스템의 다른 기능성 태양들이 상세히 설명되지 않을 수 있다. 더욱이, 다양한 도면들 내에서 도시된 연결 선들은 다양한 성분들 사이의 예시적인 기능적 관계들 및/또는 물리적 결합들을 대표하도록 의도된다. 많은 대안 또는 추가적인 기능적 관계들 또는 물리적 연결들이 실용적 시스템 내에서 존재할 수 있고, 및/또는 일부 실시예들에서 생략될 수 있다.
[69] 다수의 변형들이 가능하기 때문에 여기 설명된 구성들 및/또는 접근법들은 속성에 있어서 예시적이며, 이러한 특정한 실시예들 또는 실험예들이 제한적 의미로 인식되지 않아야 함이 이해되어야 할 것이다. 여기 설명된 특정한 루틴들 또는 방법들은 임의의 수의 공정 전략들 중 하나 또는 그 이상을 대표할 수 있다. 따라서, 도시된 다양한 행위들은 도시된 순서들 내에서, 다른 순서들 내에서 수행될 수 있고, 일부 경우들에서 생략될 수 있다.
[70] 본 개시의 기술적 사상은 여기에 개시된 다양한 공정들, 시스템들, 및 구성들, 및 다른 피쳐들, 기능들, 행위들, 및/또는 특성들의 모든 신규하고 비자명한 조합 및 부조합들뿐 아니라 이들의 임의의 및 모든 등가물들을 포함한다.

Claims (20)

  1. 금속을 포함하는 막을 선택적으로 형성하는 방법으로서,
    반응 챔버 내에 공정을 위한 기판을 제공하고, 적어도 가스와 접촉하기 위한 핫 와이어 성분을 제공하는 단계;
    상기 기판을 금속 전구체에 노출시키는 단계; 및
    상기 기판을 상기 핫 와이어의 인접부(vicinity)에 노출되었던 가스에 노출시키는 단계;를 포함하고,
    상기 기판은 적어도 두 개의 다른 물질들을 포함하고, 상기 금속막은 상기 표면들 중 하나 내에 선택적으로 형성되는 것을 특징으로 하는 방법.
  2. 청구항 1에 있어서,
    상기 금속 전구체는 전이 금속 원소를 포함하는 것을 특징으로 하는 방법.
  3. 청구항 1에 있어서,
    상기 금속 전구체는 텅스텐-함유 전구체 또는 몰리브덴-함유 전구체를 포함하는 것을 특징으로 하는 방법.
  4. 청구항 1에 있어서,
    상기 가스는 수소를 포함하는 것을 특징으로 하는 방법.
  5. 청구항 1에 있어서,
    상기 선택적으로 형성된 막은 금속성 물질을 포함하는 것을 특징으로 하는 방법.
  6. 청구항 1에 있어서,
    상기 가스가 상기 핫 와이어의 인접부에 노출되었을 때 여기된 종, 래디칼 또는 원자 종이 상기 가스로부터 형성되는 것을 특징으로 하는 방법.
  7. 청구항 1에 있어서,
    상기 기판은 제1 표면 및 제2 표면을 포함하는 것을 특징으로 하는 방법.
  8. 청구항 7에 있어서,
    상기 제1 표면은 전이 금속을 포함하는 것을 특징으로 하는 방법.
  9. 청구항 7에 있어서,
    상기 제1 표면은 산화된 금속을 포함하고, 상기 산화된 금속 아래에 원소 금속 또는 금속성 도전막이 위치하는 것을 특징으로 하는 방법.
  10. 청구항 7에 있어서,
    상기 제2 표면은 Si-O 결합들을 포함하는 것을 특징으로 하는 방법.
  11. 청구항 7에 있어서,
    상기 제2 표면은 실리콘 산화물, 실리콘 질화물, 실리콘 카바이드, 실리콘 산질화물, 실리콘 이산화물, 또는 이들의 혼합물들을 포함하는 것을 특징으로 하는 방법.
  12. 청구항 7에 있어서,
    상기 막은 상기 제1 표면 상에 선택적으로 형성되는 것을 특징으로 하는 방법.
  13. 청구항 1에 있어서,
    상기 기판을 상기 금속 전구체에 노출시키는 단계들 이후에, 상기 기판을 퍼지 가스에 노출시키는 단계를 더 포함하는 방법.
  14. 청구항 1에 있어서,
    선택비는 50% 이상인 것을 특징으로 하는 방법.
  15. 청구항 1에 있어서,
    상기 막의 두께는 1 nm 이상인 것을 특징으로 하는 방법.
  16. 청구항 1에 있어서,
    상기 반응 챔버 내의 벽은 핫 월(hot wall)인 것을 특징으로 하는 방법.
  17. 청구항 1에 있어서,
    상기 막을 선택적으로 형성하는 단계는 ALD 공정을 포함하는 것을 특징으로 하는 방법.
  18. 청구항 1에 있어서,
    상기 막을 선택적으로 형성하는 단계는 사이클(cyclic) 공정을 포함하는 것을 특징으로 하는 방법.
  19. 청구항 1에 있어서,
    상기 막을 선택적으로 형성하는 단계는 사이클 또는 순차적 CVD 공정을 포함하는 것을 특징으로 하는 방법.
  20. 청구항 1의 방법을 수행하도록 구성된 반응 챔버.
KR1020170087308A 2016-07-19 2017-07-10 텅스텐의 선택적 퇴적 KR102204364B1 (ko)

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