KR100449028B1 - 원자층 증착법을 이용한 박막 형성방법 - Google Patents

원자층 증착법을 이용한 박막 형성방법 Download PDF

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KR100449028B1
KR100449028B1 KR10-2002-0011671A KR20020011671A KR100449028B1 KR 100449028 B1 KR100449028 B1 KR 100449028B1 KR 20020011671 A KR20020011671 A KR 20020011671A KR 100449028 B1 KR100449028 B1 KR 100449028B1
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reactant
gas
chamber
film
sibn
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김영석
이상인
형용우
강만석
안재영
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삼성전자주식회사
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Abstract

본 발명은 원자층 증착법을 이용하여 우수한 스텝커버리지와 균일도 특성을 갖으며, 식각특성을 개선할 수 있는 저유전율의 SiBN막을 형성하는 방법에 관한 것이다.
본 발명은 4단계의 증착공정을 1사이클로 하여 소정횟수 반복하여 3원의 박막을 소정두께로 증착하는 방법으로서, 제1단계는 챔버로 제1반응물과 제2반응물을 주입하여 상기 웨이퍼의 표면상에 흡착시키고, 제2단계는 제3반응물을 상기 챔버로 주입하여 반응하지 않고 남아있는 제1반응물과 2반응물을 배기시킨다. 제3단계는 제4반응물을 상기 챔버로 주입하되 플라즈마를 이용하여 분해시켜 상기 1반응물 및 제2반응물과 반응속도를 향상시켜 실리콘 보론 나이트라이드막(SiBN)을 형성시키고, 제4단계는 제5반응물을 상기 챔버로 주입하여 반응하지 않고 남아있는 제4반응물과 반응부산물을 배기시킨다.
상기 SiBN막에서, 제1반응물은 BCl3, BBr3, B2H6또는 BF3개스중 하나이고, 제2반응물은 SiH2Cl2, SiCl4, Si2Cl6, 또는 SiH4개스중 하나이고, 제3 및 제5반응물은 비활성개스 또는 N2개스이며, 제4반응물은 NH3또는 N2H4개스중 하나를 사용하거나 또는 N2, H2, NH3및 이들의 혼합개스를 래디칼 형태로 사용한다.
그러므로, 본 발명에서는 원자층 증착법을 이용하여 SiBN 막을 형성하여 줌으로써, 스텝커버리지와 균일도 특성을 향상시킬 수 있으며, RIE 식각특성 및 고온 습식케미칼에 대한 식각특성을 개선할 수 있는 이점이 있다.

Description

원자층 증착법을 이용한 박막 형성방법{Method for forming thin film using ALD}
본 발명은 반도체 장치의 박막 형성방법에 관한 것으로서, 보다 구체적으로는 원자층 증착법을 이용하여 우수한 스텝 커버리지 특성과 균일도 특성을 갖으며, 개선된 식각특성을 갖는 저유전율의 실리콘 보론 나이트라이드막(SiBN)을 형성하는방법에 관한 것이다.
반도체 제조공정중에 사용되는 절연물질중 LPCVD법(Low Pressure Chemical Vapor Deposition)으로 증착된 실리콘 나이트라이드막(SiNx)은 실리콘 산화막에 대한 RIE(reactive ion etching) 및 습식식각에 대한 우수한 선택비, 내마모성과 내산화성 및 확산 배리어로서의 특성 때문에 광범위하게 사용되어 왔다. 그러나, 이러한 SiNx 막은 유전상수가 7로서 높기 때문에, 소자의 크기가 축소됨에 따라 기생 캐패시턴스가 증가하여 전달지연(propagation delay)을 유발하는 문제점이 있었다.
최근, 반도체 소자의 절연막으로 LPCVD SiNx 막 대신에 낮은 유전상수를 갖는 보론 나이트라이드막(BN)이 사용되었다. BN 막은 원자층 증착법(atomic layer deposition)을 이용하여 200 내지 550℃의 저온에서 증착하므로써, 컨퍼멀한 보론 나이트라이드막(conformal stoichiometric boron nitride)을 형성할 수 있었다.
ALD 방법으로 증착된 BN막은 증착조건에 따라 2.2 내지 5 정도의 낮은 유전율을 가지므로, 유전율이 7인 SiNx 막에 비하여 기생 캐패시턴스를 감소시켜 전달지연을 감소시킬 수 있었다.
그러나, ALD 방법으로 증착된 BN 막은 공기중의 수분에 의해서도 쉽게 가수분해되고, 황산 베이스(H2SO4base)의 고온 습식 케미칼에 쉽게 식각되는 특성을 갖으며, 또한 내산화성(oxidation resistance) 등이 좋지 않은 문제점이 있다.
또한, 종래에는 SiBN 막을 대부분 PECVD(Plasma Enhanced Chemical Vapor Deposition)법으로 증착하였기 때문에, 스텝 커버리지 특성이 열악한 문제점이 있었다.
본 발명의 목적은 상기한 바와 같은 종래 기술의 문제점을 해결하기 위한 것으로서, 원자층 증착법을 이용하여 우수한 스텝커버리지와 균일도 특성을 갖는 SiBN 막을 형성하는 방법을 제공하는 데 그 목적이 있다.
본 발명은 고온습식 케미칼에 대한 낮은 식각율 및 저유전율을 갖는 SiBN 막을 형성하는 방법을 제공하는 데 그 목적이 있다.
또한, 본 발명은 우수한 RIE 특성을 갖는 SiBN 막을 형성하는 방법을 제공하는 데 그 목적이 있다.
도 1은 본 발명의 실시예에 따른 SiBN 막을 형성하기 위한 개스의 공급 시퀀스를 보여주는 도면,
도 2는 본 발명의 실시예에 따른 SiBN 막의 FT-IR 분석결과를 보여주는 도면,
도 3은 본 발명의 실시예에 따른 SiBN 막의 RIE 식각율을 보여주는 도면,
도 4는 본 발명의 실시예에 따른 SiBN 막의 고온습케미칼에 대한 식식각율을 보여주는 도면,
도 5는 본 발명의 실시예에 따른 SiN 막의 스텝커버리지를 보여주는 도면,
도 6은 본 발명의 실시예에 따른 SiBN 막의 유전율를 보여주는 도면,
이와 같은 목적을 달성하기 위한 본 발명은 챔버에 웨이퍼를 로딩하는 단계와; 상기 챔버로 제1반응물과 제2반응물을 주입하여 상기 웨이퍼의 표면상에 흡착시키는 제1단계와; 제3반응물을 상기 챔버로 주입하여 반응하지 않고 남아있는 제1반응물과 2반응물을 배기시키는 제2단계와; 제4반응물을 상기 챔버로 주입하되 플라즈마를 이용하여 분해시켜 상기 1반응물 및 제2반응물과 반응속도를 향상시켜 실리콘 보론 나이트라이드막(SiBN)을 형성하는 제3단계와; 제5반응물을 상기 챔버로 주입하여 반응하지 않고 남아있는 제4반응물과 반응부산물을 배기시키는 제4단계와; 상기 제1단계 내지 제4단계를 1사이클로 하여 소정횟수만큼 반복 진행하여 3원 박막을 증착하는 제5단계를 포함하는 원자층 증착법을 이용한 박막 형성방법을 제공하는 것을 특징으로 한다.
상기 제1반응물은 BCl3, BBr3, B2H6또는 BF3개스중 하나이고, 제2반응물은 SiH2Cl2, SiCl4, Si2Cl6, 또는 SiH4개스중 하나이며, 제3 및 제5반응물은 비활성개스 또는 N2개스이고, 제4반응물은 NH3또는 N2H4개스중 하나를 사용하거나 또는 N2, H2, NH3및 이들의 혼합개스를 래디칼 형태로 사용한다. 이때, 제4반응물을 ICP, DC, RF 또는 마이크로 웨이브 플라즈마를 이용하여 분해시켜 제1 및 제2반응물과의 반응속도를 향상시킨다.
이하, 본 발명을 보다 구체적으로 설명하기 위하여 본 발명에 따른 실시예를 첨부 도면을 참조하여 설명한다.
도 1은 본 발명의 실시예에 따른 SiBN 막을 증착하기 위한 개스의 공급시퀀스를 도시한 것이다.
도 1을 참조하여 본 발명의 SiBN 막을 ALD 방법으로 증착하는 방법을 설명하면 다음과 같다.
먼저, 내부의 압력을 대기압 이하로 유지할 수 있도록 펌프를 구비한 챔버(도면상에는 도시되지 않음)내에 SiBN 막이 증착될 웨이퍼, 예를 들면 단결정 실리콘 기판을 로딩하고 200 내지 750℃의 온도로 가열하여, SiBN 막을 증착하기 위한 사이클을 일정횟수만큼 진행한다.
먼저, 제1단계로, 소오스 개스로서 일정분압의 제1개스와 제2개스를 일정시간동안 챔버로 주입하여, 웨이퍼 표면상에 제1개스와 제2개스가 충분히 흡착되어포화되도록 한다. 이때, 제1개스는 BCl3, BBr3, B2H6또는 BF3중 하나이고, 제2개스는 dichlorosilane(DCS, SiH2Cl2), hexa-chlorosilane(HCD, Si2Cl6), SiCl4, SiCl6, 또는 silane(SiH4) 중 하나이다.
제2단계로, 제3개스, 예를 들면 Ar, He 등과 같은 비활성 개스 또는 N2개스를 챔버로 주입하여 챔버내에 반응하지 않고 남아있는 제1개스 및 제2개스를 배기(pump out)시킨다. 이로써, 제1개스 및 제2개스의 분압이 낮아진다.
제3단계로, 일정 분압의 제4개스, 예를 들면 NH3또는 N2H2개스 등과 같은 반응개스를 일정시간동안 챔버로 주입하여 기판표면에 흡착되어 있는 제1개스 및 제2개스와 반응시켜 줌으로써, 실리콘원자(Si), 보론원자(B) 및 질소원자(N)로 이루어진 SiBN 의 단원자층(monolayer)을 형성한다.
제3단계에서, ICP(Inductive Coupled Plasma), DC, RF, 마이크로 웨이브 플라즈마를 이용하여 재4개스를 분해시켜 반응속도를 증가시킬 수 도 있다. 이때, 제4개스로는 NH3또는 N2H4개스중 하나를 사용하거나 또는 N2, H2, NH3및 이들의 혼합개스를 래디칼 형태로 사용할 수도 있다.
제4단계로, 제5개스, Ar, He 등과 같은 비활성 개스 또는 N2개스를 챔버로 주입하여 챔버안에 반응하지 않고 남아있는 제4개스 뿐만 아니라 HCl 등과 같은 반응 부산물을 배기시킨다. 이로써, 챔버내의 제4개스의 분압이 충분히 낮아진다.
상기한 바와같이 SiBN 단원자층(monolayer)의 증착공정은 4단계로 이루어지고, 이러한 단원자층을 증착하기 위한 4단계공정을 1사이클로 하여 소정두께를 갖는 SiBN막을 형성한다. 즉, 1사이클당 ALD 방식에 의해 증착되는 SiBN 막의 증착두께는 일정하므로, 원하는 두께의 SiBN 막을 얻기 위해서는 일정횟수의 사이클을 반복 진행한다.
제2단계와 제4단계에서 비활성개스 또는 N2개스를 주입하여 반응하지 않고 남아있는 개스 또는 반응 부산물을 배기시키는 경우, 본 발명의 실시예에서와 같이 1사이클 내내 비활성개스 또는 N2개스를 주입하여 배기시키거나 또는 제2단계와 제4단계에서만 비활성개스 또는 N2개스를 주입하여 배기시킬 수도 있다.
이때, 상기한 바와같은 방법으로 SiBN 막을 형성하기 위한 챔버의 크기는 약 7리터(liter) 정도이고, 웨이퍼의 온도는 대략 400 내지 600℃, 압력은 1 내지 3torr 이다.
도 2는 본 발명의 실시예에 따른 SiBN막의 FT-IR(Furrier transform infrared spectroscopy) 분석결과를 도시한 것이다. 전형적으로, BN막에서 B-N 밴드가 1370㎝-1이고, SiNx 막에서 Si-N 스트레칭밴드가 1860㎝-1이다. 이에 반하여, SiBN 막은 도 2에 도시된 바와같이, B-N 밴드가 1310㎝-1, Si-N 스트레칭 밴드가 910㎝-1에서 각각 관찰되므로, Si, B 및 N 원자로 이루어진 3원막(ternary)의 SiBN 막이 형성됨을 알 수 있다.
도 3과 도 4는 본 발명의 실시예에 따른 3원 SiBN 막의 RIE 식각율과 고온습식 케미칼에 대한 식각율을 각각 도시한 것이다. C5F8/CH2F2/AR/CO/O2의 식각조건에서 LPCVD SiNx 막과 유사한 우수한 RIE 식각특성을 얻을 수 있을 뿐만 아니라, H2SO4또는 SC1과 같은 습식식각 케미칼에 대한 우수한 선택비를 얻을 수 있음을 알 수 있다.
도 5는 본 발명의 실시예에 따른 3원 SiBN 막의 스텝커버리지특성을 보여주는 사진으로서, 95% 이상의 양호한 스텝커버리지를 얻을 수 있다.
도 6은 본 발명의 실시예에 따른 3원 SiBN 막의 유전율을 도시한 것으로서, 유전율 7의 LPCVD SiNx 막에 비하여 SiBN막은 4.4정도의 저유전율을 갖는다.
상기한 바와같은 본 발명에 따르면, 반도체 소자의 절연막으로 SiBN 막을 원자층 증착법으로 형성하여 줌으로써, 스텝 커버리지와 균일도를 향상시킬 수 있으며, RIE 식각율 및 고온 케미칼에 대한 식각율을 개선시킬 수 있다. 또한, 본 발명은 저유전율을 갖는 SiBN 막을 형성하여 줌으로써, 기생 캐패시턴스를 감소시켜 전달지연을 개선시킬 수 있는 이점이 있다.
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구의 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.

Claims (8)

  1. 챔버에 웨이퍼를 로딩하는 단계와;
    상기 챔버로 제1반응물과 제2반응물을 주입하여 상기 웨이퍼의 표면상에 흡착시키는 제1단계와;
    제3반응물을 상기 챔버로 주입하여 반응하지 않고 남아있는 제1반응물과 2반응물을 배기시키는 제2단계와;
    제4반응물을 상기 챔버로 주입하되 플라즈마를 이용하여 분해시켜 상기 1반응물 및 제2반응물과 반응속도를 향상시켜 실리콘 보론 나이트라이드막(SiBN)을 형성하는 제3단계와;
    제5반응물을 상기 챔버로 주입하여 반응하지 않고 남아있는 제4반응물과 반응부산물을 배기시키는 제4단계와;
    상기 제1단계 내지 제4단계를 1사이클로 하여 소정횟수만큼 반복 진행하여 3원 박막을 증착하는 제5단계를 포함하는 것을 특징으로 하는 원자층 증착법을 이용한 박막 형성방법.
  2. 삭제
  3. 제1항에 있어서, 상기 제1반응물은 BCl3, BBr3, B2H6또는 BF3개스중 하나인것을 특징으로 하는 반도체 장치의 절연막 형성방법.
  4. 제1항에 있어서, 상기 제2반응물은 SiH2Cl2, SiCl4, Si2Cl6, 또는 SiH4개스중 하나인 것을 특징으로 하는 반도체 장치의 절연막 형성방법.
  5. 제1항에 있어서, 상기 제3 및 제5반응물은 비활성개스 또는 N2개스인 것을 특징으로 하는 반도체 장치의 절연막 형성방법.
  6. 제1항에 있어서, 제4반응물은 NH3또는 N2H4개스중 하나를 사용하거나 또는 N2, H2, NH3및 이들의 혼합개스를 래디칼 형태로 사용하는 것을 특징으로 하는 반도체 장치의 절연막 형성방법.
  7. 제1항에 있어서, 제4반응물 플라즈마는 ICP, DC, RF 또는 마이크로 웨이브 플라즈마 공정 중 어느하나를 적용하는 것을 특징으로 하는 반도체 장치의 절연막 형성방법.
  8. 제1항에 있어서, 상기 웨이퍼의 온도는 400 내지 600℃이고, 증착압력은 1 내지 3torr 인 것을 특징으로 하는 반도체 장치의 절연막 형성방법.
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