KR100385947B1 - 원자층 증착 방법에 의한 박막 형성 방법 - Google Patents

원자층 증착 방법에 의한 박막 형성 방법 Download PDF

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KR100385947B1
KR100385947B1 KR10-2000-0073807A KR20000073807A KR100385947B1 KR 100385947 B1 KR100385947 B1 KR 100385947B1 KR 20000073807 A KR20000073807 A KR 20000073807A KR 100385947 B1 KR100385947 B1 KR 100385947B1
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South Korea
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reactant
thin film
adsorption layer
supplying
halogen group
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KR10-2000-0073807A
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KR20020044422A (ko
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이승환
김영관
김동찬
박영욱
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삼성전자주식회사
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Priority to KR10-2000-0073807A priority Critical patent/KR100385947B1/ko
Priority to US09/871,430 priority patent/US6468924B2/en
Publication of KR20020044422A publication Critical patent/KR20020044422A/ko
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    • H—ELECTRICITY
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    • H01L21/04—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
    • 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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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
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    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3

Abstract

ALD 방법을 이용하여 반도체 기판상에 박막을 형성할 때 박막 내의 불순물 발생 및 피티클 소스 발생을 억제하기 위하여 활성화된 수소 가스를 공급하는 박막 형성 방법에 관하여 개시한다. 본 발명에서는 반도체 기판상에 할로겐족 원소를 함유하는 제1 반응물을 공급하여 할로겐족 원소가 결합된 제1 반응물 흡착층을 상기 반도체 기판상에 화학흡착시킨다. 상기 제1 반응물 흡착층이 형성된 결과물상에 활성화된 수소 가스를 공급하여 상기 제1 반응물 흡착층으로부터 할로겐족 원소를 제거한다. 상기 할로겐족 원소가 제거된 제1 반응물 흡착층에 제2 반응물을 공급하여 제2 반응물 흡착층을 화학흡착시켜서 고체 박막을 형성한다.

Description

원자층 증착 방법에 의한 박막 형성 방법{Method of forming thin film by atomic layer deposition}
본 발명은 반도체 소자의 제조 방법에 관한 것으로, 특히 반도체 소자 제조에 필요한 박막을 원자층 증착(atomic layer deposition: 이하, "ALD"라 함) 방법에 의하여 형성하는 방법에 관한 것이다.
일반적으로, 박막은 반도체 소자의 유전막, 액정 표시 소자의 투명한 도전체, 및 전자 발광 박막 표시 소자(electroluminescent thin film display)의 보호층 등으로 다양하게 사용된다.
특히, 반도체 소자의 유전막으로 쓰이는 박막은 높은 커패시턴스를 확보하고 누설 전류를 억제하기 위하여 유전막 내부 및 계면에서 불순물 또는 결함이 없어야 한다. 또한, 형성된 박막의 스텝 커버리지(step coverage) 및 균일도(uniformity)가 좋아야 한다.
그러나, 통상의 CVD(Chemical Vapor Deposition) 또는 PVD(Physical Vapor Deposition) 방법을 이용하여 박막을 형성하면 우수한 스텝 커버리지를 얻기가 어렵다. 특히, 통상의 CVD 방법에 있어서는, 서피스 카이네틱 모드(surface kinetic mode)를 활용하는 증착 공정에 의하여 비교적 우수한 스텝 커버리지를 갖는 유전막을 얻을 수는 있으나, 유전막 증착에 필요한 반응물들이 기판상에 동시에 전달되므로 특정한 부분에서의 스텝 커버리지를 필요에 따라 조절하기가 어렵다.
근래, 상기와 같은 문제를 극복하기 위하여, 박막을 형성할 기판 표면에 반응물들을 주기적으로 공급하여 서피스 카이네틱 영역을 활성화시킴으로써 전체적으로 우수한 스텝 커버리지를 얻을 수 있는 박막 형성 방법들이 제안되었다. 이들 방법으로는 예를 들면 ALD, 사이클릭(cyclic) CVD, 디지털 (digital) CVD, 어드밴스드(advanced) CVD 등과 같은 방법이 있다.
반도체 소자 제조시 필요한 박막을 형성하기 위하여 벌크 상태에서 우수한특성을 제공하는 박막 재료를 반도체 소자의 제조 공정에 도입하기 위하여는 박막으로 형성된 후에도 그 물질의 우수한 특성을 유지시킬 수 있는 박막 제조 기술이 필요하다. 그러나, 상기 방법들을 이용하여 박막을 제조하는 경우, 반응물을 구성하는 케미칼 리간드(chemical ligand)에 함유되어 있는 불필요한 원자가 박막 내에 잔류하여 불순물로 되거나 기판 표면에서 파티클을 유발시키는 원인으로 될 수 있다. 박막 제조 과정에서 발생되는 부산물은 박막 내의 불순물 또는 파티클을 콘트롤하는 데 큰 영향을 준다.
상기 언급된 박막 형성 기술들에서는 박막 재료로서 필요한 원소를 높은 증기압 상태로 박막이 형성된 기판상에 전달한다. 따라서, 일반적으로 기판상에 필요한 요소 만을 전달하는 것이 아니라 유기금속 전구체 (metalorganic precursor), 금속 할로겐화물 (metal halides) 등과 같은 형태의 반응물로 증기를 기판상에 전달한다. 형성하고자 하는 박막 내의 불순물을 최소화하기 위하여, 상기와 같이 기판상에 전달되는 반응물중에서 금속 원소와 유기 리간드 (organic ligand) 또는 할로겐화물(halides)은 CVD 방법에서는 분해(decomposition)에 의하여 제거되지만, ALD 방법에서는 화학 치환(chemical exchange)에 의하여 제거된다. 즉, ALD 방법에서는 필요한 소스 가스들이 반응 챔버 내에서 혼합되지 않고 한 종류씩 펄스(pulse) 방식으로 유입된다. 예를 들면, 제1 소스 가스 및 제2 소스 가스를 사용하여 박막을 형성하는 경우에는, 먼저 반응 챔버 내에 제1 소스 가스 만을 유입시켜서 기판상에 상기 제1 소스 가스를 화학 흡착(chemisorption)시키고, 그 후 제2 소스 가스를 반응 챔버 내에 유입시켜서 상기 제2 소스 가스를 기판상에 화학흡착시키는 방법에 의하여 원자층으로 이루어지는 박막을 형성한다.
예를 들면, SiCl4와 NH3로부터 형성되는 Si3N4박막은 다음과 같은 반응을 거쳐 CVD 또는 ALD 방법에 의하여 형성된다.
3SiCl4+ 4NH3→ Si3N4+ 12HCl
이 때, CVD 방법에서는 550℃ 이상의 온도로 유지되는 기판상에 SiCl4및 NH3가 동시에 전달되며, 열분해(thermal decomposition)에 의하여 Si3N4박막 형성과 함께 HCl이 부산물로 생성된다. 한편, ALD 방법에서는 400℃ 이상의 비교적 저온으로 유지되는 기판상에 SiCl4가 화학흡착되고, 그 위에 NH3가 전달되어 화학 치환에 의하여 1층의 Si3N4층이 형성됨과 동시에 HCl이 부산물로 형성된다.
상기와 같이 발생된 HCl 부산물은 반응 가스로서 공급되는 NH3와 반응하여 NH4Cl을 형성한다. 따라서, 상기와 같은 공정은 빈번한 세정 공정을 요할 뿐 만 아니라 반도체 제조 장치의 다운 타임(down time)을 증가시키는 요인으로 작용한다. 또한, 상기와 같이 형성되는 NH4Cl에 의하여 박막 제조 공정중에 파티클이 다량 발생되고, 전기적 특성이 열화된다.
본 발명은 상기한 종래 기술에서의 문제점을 해결하고자 하는 것으로, 본 발명의 목적은 반도체 소자를 제조하기 위하여 비교적 저온 공정에 의하여 우수한 스텝 커버리지를 갖는 박막을 형성함에 있어서 상기 박막 내에 불순물에 의한 파티클발생을 억제할 수 있는 박막 형성 방법을 제공하는 것이다.
도 1a 내지 도 1f는 본 발명의 바람직한 실시예에 따른 박막 형성 방법을 설명하기 위하여 공정 순서에 따라 도시한 단면도들이다.
도 2a 내지 도 2f는 본 발명에 따른 박막 형성 방법에 의하여 실리콘 질화막을 형성하는 방법을 설명하기 위한 단면도들이다.
도 3은 본 발명에 따른 박막 형성 방법에 따라 실리콘 질화막을 형성할 때 적용된 가스 펄싱 방법을 나타낸 타이밍도이다.
<도면의 주요 부분에 대한 부호의 설명>
10: 반도체 기판, 12: 제1 반응물, 20: 제1 반응물 흡착층, 22: 할로겐족 원소가 제거된 흡착층, 24: 고체 박막, 32: 불활성 가스, 34: 활성화된 수소 가스, 36: 불활성 가스, 42: 제2 반응물, 44: 불활성 가스.
상기 목적을 달성하기 위하여, 본 발명의 일 양태에 따른 박막 형성 방법에서는, 반도체 기판상에 할로겐족 원소를 함유하는 제1 반응물을 공급하여 할로겐족 원소가 결합된 제1 반응물 흡착층을 상기 반도체 기판상에 화학흡착시킨다. 상기 제1 반응물 흡착층이 형성된 결과물상에 활성화된 수소 가스를 공급하여 상기 제1 반응물 흡착층으로부터 할로겐족 원소를 제거한다. 상기 할로겐족 원소가 제거된 제1 반응물 흡착층에 제2 반응물을 공급하여 제2 반응물 흡착층을 화학흡착시켜서 고체 박막을 형성한다.
상기 수소 가스 공급 단계는 리모트-플라즈마(remote-plasma)에 의해 활성화시키는 단계를 포함한다.
상기 고체 박막으로서 단원자 질화물, 복합 질화물, 단원자 산화물 또는 복합 산화물을 형성할 수 있다.
본 발명의 일 양태에 따른 박막 형성 방법은 상기 활성화된 수소 가스를 공급하기 전에 상기 제1 반응물 흡착층이 형성된 결과물상의 부산물을 제거하는 단계를 더 포함할 수 있다. 또한, 상기 제2 반응물을 공급하기 전에 상기 제1 반응물 흡착층으로부터 할로겐족 원소가 제거된 결과물상의 부산물을 제거하는 단계를 더 포함할 수 있다. 또한, 상기 고체 박막이 형성된 결과물상의 부산물을 제거하는 단계를 더 포함할 수 있다. 상기 부산물을 제거하기 위하여 불활성 가스를 사용한 퍼지(purge) 또는 펌핑(pumping)을 이용할 수 있다.
본 발명의 일 양태에 따른 박막 형성 방법에서는 원하는 두께의 박막이 얻어질 때까지 상기 제1 반응물 공급 단계, 상기 활성화된 수소 가스 공급 단계, 및 상기 제2 반응물 공급 단계를 순차적으로 복수회 반복할 수 있다.
또한, 본 발명의 다른 양태에 따른 박막 형성 방법에서는, 반도체 기판상에 할로겐족 원소를 함유하는 실리콘 소스 가스를 공급하여 할로겐족 원소가 결합된 실리콘 흡착층을 상기 반도체 기판상에 화학흡착시킨다. 상기 실리콘 흡착층이 형성된 결과물상에 활성화된 수소 가스를 공급하여 상기 실리콘 흡착층으로부터 할로겐족 원소를 제거한다. 상기 할로겐족 원소가 제거된 실리콘 흡착층에 질소 소스 가스를 공급하여 실리콘 질화막을 형성한다.
본 발명에 의하면, NH4Cl과 같은 파티클 소스가 생성되는 것이 효과적으로 방지되며, 얻어진 박막 내에 염소 원자와 같은 불순물을 함유하지 않도록 하면서 비교적 저온에서 우수한 스텝 커버리지를 갖는 박막을 형성할 수 있다.
다음에, 본 발명의 바람직한 실시예에 대하여 첨부 도면을 참조하여 상세히 설명한다.
다음에 예시하는 실시예들은 여러가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 다음에 상술하는 실시예에 한정되는 것은 아니다. 본 발명의 실시예는 당 업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위하여 제공되어지는 것이다. 첨부 도면에서 막 또는 영역들의 크기 또는 두께는 명세서의 명확성을 위하여 과장되어진 것이다. 또한, 어떤 막이 다른 막 또는 기판의 "위"에 있다라고 기재된 경우, 상기 어떤 막이 상기 다른 막의 위에 직접 존재할 수도 있고, 그 사이에 제3의 다른 막이 개재될 수도 있다.
도 1a 내지 도 1f는 본 발명의 바람직한 실시예에 따라 ALD 방법으로 박막을 형성하는 방법을 설명하기 위하여 공정 순서에 따라 도시한 단면도들이다.
도 1a를 참조하면, 반도체 소자 제조를 위하여 박막을 형성하는 데 필요한 제1 소스 가스로서 제1 반응물(12)을 반도체 기판(10)상에 공급한다. 상기 제1 반응물(12)은 통상적으로 할로겐족 원소, 예를 들면 염소 원자를 포함하는 전구체이다. 그 결과, 상기 반도체 기판(10)상에는 제1 반응물 흡착층(20)이 화학흡착된다.
상기 제1 반응물(12)은 상기 반도체 기판(10)상에 형성하고자 하는 박막의 종류에 따라 다르며, 필요에 따라 SiCl4, TiCl4, SiH2Cl2, Si2Cl6, TaCl3, AlCl3또는 Al(CH3)2Cl 등을 공급할 수 있다. 예를 들면, 상기 반도체 기판(10)상에 실리콘 질화막 또는 실리콘 산화막을 형성하고자 하는 경우에는 상기 제1 반응물(12)로서 실리콘 소스 가스인 SiCl4, SiH2Cl2또는 Si2Cl6를 공급한다. 상기 반도체 기판(10)상에 Ta2O5막을 형성하고자 하는 경우에는 상기 제1 반응물(12)로서 TaCl3를 공급할 수 있다. 또한, 상기 반도체 기판(10)상에 Al2O3막을 형성하고자 하는 경우에는 상기 제1 반응물(12)로서 AlCl3를 공급할 수 있다.
도 1b를 참조하면, 상기 제1 반응물 흡착층(20)이 화학흡착된 결과물상에 잔존하는 부산물을 제거하기 위하여 불활성 가스(32), 예를 들면 질소 가스를 공급하여 퍼지(purge)한다. 상기 부산물을 제거하기 위하여 퍼지 공정 대신펌핑(pumping) 공정을 이용할 수도 있다.
도 1c를 참조하면, 상기 제1 반응물 흡착층(20)이 형성된 결과물상에 활성화된 수소 가스(34)를 공급한다. 상기 활성화된 수소 가스(34)를 공급하기 위하여, 상기 반도체 기판(10)상에 공급되는 수소 가스를 리모트-플라즈마(remote-plasma)에 의하여 활성화시키는 단계가 추가된다. 그 결과, 상기 활성화된 수소 가스(34)로부터 공급되는 수소와 상기 제1 반응물 흡착층(20)에 결합되어 있는 할로겐족 원소가 반응함으로써 상기 제1 반응물 흡착층(20)으로부터 할로겐족 원소가 제거되어 상기 반도체 기판(10)상에는 할로겐족 원소가 제거된 흡착층(22)이 남는다.
도 1d를 참조하면, 상기 할로겐족 원소가 제거된 흡착층(22)이 남아 있는 결과물상에 잔존하는 부산물을 제거한다. 이를 위하여, 도 1b를 참조하여 설명한 바와 같이, 불활성 가스(36)를 이용하여 퍼지하거나, 또는 펌핑 공정을 이용한다.
도 1e를 참조하면, 상기 박막을 형성하는 데 필요한 제2 소스 가스로서 제2 반응물(42)을 상기 할로겐족 원소가 제거된 흡착층(22)상에 공급한다. 상기 제2 반응물(42)은 상기 반도체 기판(10)상에 형성하고자 하는 박막의 종류에 따라 적절히 선택될 수 있다. 예를 들면, 상기 반도체 기판(10)상에 실리콘 질화막을 형성하는 경우에는 상기 제2 반응물(42)로서 NH3또는 N2H4를 공급할 수 있다. 또한, 상기 잔도체 기판(10)상에 실리콘 산화막, Ta2O5막, Al2O3막과 같은 단원자 산화물로 이루어지는 산화막을 형성하고자 하는 경우에는 상기 제2 반응물(42)로서 H2O 또는 TEOS (tetraethylorthosilicate)를 공급할 수 있다.
그 결과, 상기 제2 반응물(42)의 구성 원소중 상기 박막 형성에 필요한 원소가 상기 흡착층(22)상에 화학흡착되어 고체 박막(24)이 형성된다.
도 1f를 참조하면, 상기 고체 박막(24)이 형성된 결과물상에 잔존하는 부산물을 제거한다. 이를 위하여, 도 1b를 참조하여 설명한 바와 같이, 불활성 가스(44)를 이용하여 퍼지하거나, 또는 펌핑 공정을 이용한다.
원하는 두께를 가지는 박막이 얻어질 때까지 도 1a 내지 도 1f를 참조하여 설명한 과정으로 이루어지는 하나의 사이클을 복수회 반복한다.
상기와 같은 방법으로 얻어지는 박막으로서 상기 제1 반응물(12) 및 제2 반응물(42)을 적절히 선택함으로써 SiN, TiN, TaN, AlN과 같은 단원자 질화물, WSiN, TiSiN, TaSiN, AlSiN, AlTiN과 같은 복합 질화물, Al2O3, TiO2, Ta2O5, SiO2과 같은 단원자 산화물, SrTiO3, PbTiO3, (Ba, Sr)TiO3, Pb(Zr, Ti)O3, (Pb, La)(Zr, Ti)O3과 같은 복합 산화물 등 다양한 막이 얻어질 수 있다.
도 2a 내지 도 2f는 본 발명에 따른 박막 형성 방법에 의하여 반도체 기판(100)상에 실리콘 질화막을 형성한 실험예를 공정 순서에 따라 설명하기 위한 단면도들이다.
도 2a를 참조하면, 반응 챔버(도시 생략) 내에 반도체 기판(100)을 로딩한 후, 상기 반응 챔버를 450℃의 비교적 저온으로 유지하고 챔버 압력을 1 torr 이하로 유지시킨 상태에서 실리콘 질화막을 형성하는 데 필요한 제1 소스 가스로서 실리콘 소스 가스(112), 즉 SiCl4를 60초 동안 상기 반도체 기판(100)상에 공급하였다. 이 때, 상기 반도체 기판(100)상에는 실리콘 원자가 화학흡착된 상태로 Si-Cl 결합을 포함하는 흡착층이 형성된다.
도 2b를 참조하면, 상기 Si-Cl 결합을 포함하는 흡착층이 형성된 결과물상에 N2가스(132)를 30초 동안 공급하여 퍼지함으로써 상기 반도체 기판(100)상에 잔존하는 부산물을 제거하였다.
도 2c를 참조하면, 흡착층이 형성된 결과물상에 리모트-플라즈마에 의해 활성화된 수소 가스(134)를 60초 동안 공급하여, 이로부터 공급되는 수소와 상기 흡착층에 결합된 염소 원자를 반응시켰다. 상기 활성화된 수소 가스(134)를 제공하기 위하여 인가된 RF 파워는 40watt이었다. 이 때, 염소 원자는 HCl의 형태로 되어 상기 흡착층으로부터 분리되고, 상기 반도체 기판(100)상에는 실리콘 원자로만 이루어지는 흡착층이 남게 된다.
도 2d를 참조하면, 활성화된 수소 가스(132)를 공급하고 난 후, 상기 결과물상에서 HCl를 제거하기 위하여 N2가스(136)를 30초 동안 공급하여 퍼지하였다.
도 2e를 참조하면, 실리콘 질화막을 형성하는 데 필요한 제2 소스 가스로서 질소 소스 가스(142) 즉 NH3가스를 상기 실리콘 원자로 이루어지는 흡착층상에 90초 동안 공급하여 상기 흡착층을 구성하는 실리콘과 상기 질소 소스 가스(142)로부터의 질소와의 결합을 유도하였다. 상기 질소 소스 가스(142)로서 N2H4가스를 사용하여도 같은 결과를 얻을 수 있다.
도 2f를 참조하면, 상기 질소 소스 가스(142) 공급 후 상기 반도체기판(100)상에 잔존하는 부산물들을 제거하기 위하여 N2가스(144)를 30초 동안 공급하여 퍼지하였다.
도 2a 내지 도 2f에서 설명한 바와 같은 과정을 1 사이클로 하는 실리콘 질화막 형성 방법에서 적용된 가스 펄싱 방법을 도 3에 나타내었다.
상기한 바와 같은 ALD 방법에 의한 실리콘 질화막 형성 과정을 1 사이클 진행한 결과, 상기 반도체 기판(100)상에는 염소 원자와 같은 불순물을 함유하지 않으며 Si-N 결합으로 이루어지는 실리콘 질화막이 2Å의 두께로 형성된 것을 확인하였다.
원하는 두께를 가지는 실리콘 질화막이 얻어질 때까지 도 2a 내지 도 2f를 참조하여 설명한 바와 같은 과정을 복수회 반복함으로써, 스텝 커버리지가 우수하고 불순물이 함유되지 않은 우수한 실리콘 질화막이 얻어진다. 상기 방법에 의하여 실리콘 질화막을 형성하면, NH4Cl과 같은 파티클 소스가 생성되는 것이 효과적으로 방지된다.
본 발명에 따른 박막 형성 방법에서는 ALD 방법에 의하여 반도체 기판상에 원하는 박막을 형성하기 위하여, 먼저 제1 반응 가스를 공급한 후 퍼지에 의하여 부산물들을 제거하고, 활성화된 수소 가스를 공급하여 반도체 기판상에 결합되어 있는 할로겐족 원소를 제거한다. 따라서, 그 후 박막 형성에 필요한 제2 반응 가스를 공급하였을 때 NH4Cl과 같은 파티클 소스가 생성되는 것이 효과적으로 방지된다.또한, 얻어진 박막 내에 염소 원자와 같은 불순물을 함유하지 않도록 하면서 비교적 저온에서 우수한 스텝 커버리지를 갖는 박막을 형성할 수 있다.
이상, 본 발명을 바람직한 실시예를 들어 상세하게 설명하였으나, 본 발명은 이에 한정되지 않고, 본 발명의 기술적 사상의 범위 내에서 당 분야에서 통상의 지식을 가진 자에 의하여 여러 가지 변형이 가능하다.

Claims (25)

  1. 반도체 기판상에 할로겐족 원소를 함유하는 제1 반응물을 공급하여 할로겐족 원소가 결합된 제1 반응물 흡착층을 상기 반도체 기판상에 화학흡착시키는 단계와,
    상기 제1 반응물 흡착층이 형성된 결과물상에 리모트-플라즈마(remote-plasma)에 의해 활성화된 수소 가스를 공급하여 상기 제1 반응물 흡착층으로부터 할로겐족 원소를 제거하는 단계와,
    상기 할로겐족 원소가 제거된 제1 반응물 흡착층에 제2 반응물을 공급하여 제2 반응물 흡착층을 화학흡착시켜서 고체 박막을 형성하는 단계를 포함하는 것을 특징으로 하는 박막 형성 방법.
  2. 제1항에 있어서, 상기 할로겐족 원소는 염소 원자인 것을 특징으로 하는 박막 형성 방법.
  3. 제1항에 있어서, 상기 제1 반응물은 SiCl4, TiCl4, SiH2Cl2, Si2Cl6, TaCl3,AlCl3또는 Al(CH3)2Cl인 것을 특징으로 하는 박막 형성 방법.
  4. 삭제
  5. 제1항에 있어서, 상기 고체 박막은 단원자 질화물, 복합 질화물, 단원자 산화물 또는 복합 산화물인 것을 특징으로 하는 박막 형성 방법.
  6. 제5항에 있어서, 상기 단원자 질화물은 SiN, TiN, TaN, 또는 AlN인 것을 특징으로 하는 박막 형성 방법.
  7. 제5항에 있어서, 상기 복합 질화물은 WSiN, TiSiN, TaSiN, AlSiN 또는 AlTiN인 것을 특징으로 하는 박막 형성 방법.
  8. 제5항에 있어서, 상기 단원자 산화물은 Al2O3, TiO2, Ta2O5또는 SiO2인 것을 특징으로 하는 박막 형성 방법.
  9. 제5항에 있어서, 상기 복합 산화물은 SrTiO3, PbTiO3, (Ba, Sr)TiO3, Pb(Zr,Ti)O3또는 (Pb, La)(Zr, Ti)O3인 것을 특징으로 하는 박막 형성 방법.
  10. 제1항에 있어서, 상기 활성화된 수소 가스를 공급하기 전에 상기 제1 반응물 흡착층이 형성된 결과물상의 부산물을 제거하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  11. 제1항에 있어서, 상기 제2 반응물을 공급하기 전에 상기 제1 반응물 흡착층으로부터 할로겐족 원소가 제거된 결과물상의 부산물을 제거하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  12. 제1항에 있어서, 상기 고체 박막이 형성된 결과물상의 부산물을 제거하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  13. 제10항 내지 제12항중 어느 한 항에 있어서, 상기 부산물 제거 단계는 불활성 가스를 사용한 퍼지(purge)에 의하여 행하는 것을 특징으로 하는 박막 형성 방법.
  14. 제10항 내지 제12항중 어느 한 항에 있어서, 상기 부산물 제거 단계는 펌핑(pumping)에 의하여 행하는 것을 특징으로 하는 박막 형성 방법.
  15. 제1항에 있어서, 원하는 두께의 박막이 얻어질 때까지 상기 제1 반응물 공급 단계, 상기 활성화된 수소 가스 공급 단계, 및 상기 제2 반응물 공급 단계를 순차적으로 복수회 반복하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  16. 반도체 기판상에 할로겐족 원소를 함유하는 실리콘 소스 가스를 공급하여 할로겐족 원소가 결합된 실리콘 흡착층을 상기 반도체 기판상에 화학흡착시키는 단계와,
    상기 실리콘 흡착층이 형성된 결과물상에 리모트-플라즈마에 의해 활성화된 수소 가스를 공급하여 상기 실리콘 흡착층으로부터 할로겐족 원소를 제거하는 단계와,
    상기 할로겐족 원소가 제거된 실리콘 흡착층에 질소 소스 가스를 공급하여 실리콘 질화막을 형성하는 단계를 포함하는 것을 특징으로 하는 박막 형성 방법.
  17. 제16항에 있어서, 상기 실리콘 소스 가스는 SiCl4, SiH2Cl2또는 Si2Cl6인 것을 특징으로 하는 박막 형성 방법.
  18. 삭제
  19. 제16항에 있어서, 상기 질소 소스 가스는 NH3또는 N2H4인 것을 특징으로 하는 박막 형성 방법.
  20. 제16항에 있어서, 상기 활성화된 수소 가스를 공급하기 전에 상기 실리콘 흡착층이 형성된 결과물상의 부산물을 제거하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  21. 제16항에 있어서, 상기 질소 소스 가스를 공급하기 전에 상기 실리콘 흡착층으로부터 할로겐족 원소가 제거된 결과물상의 부산물을 제거하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  22. 제16항에 있어서, 상기 실리콘 질화막이 형성된 결과물상의 부산물을 제거하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
  23. 제20항 내지 제22항중 어느 한 항에 있어서, 상기 부산물 제거 단계는 불활성 가스를 사용한 퍼지에 의하여 행하는 것을 특징으로 하는 박막 형성 방법.
  24. 제20항 내지 제22항중 어느 한 항에 있어서, 상기 부산물 제거 단계는 펌핑에 의하여 행하는 것을 특징으로 하는 박막 형성 방법.
  25. 제16항에 있어서, 원하는 두께의 박막이 얻어질 때까지 상기 실리콘 소스 가스 공급 단계, 상기 활성화된 수소 가스 공급 단계, 및 상기 질소 소스 가스 공급 단계를 순차적으로 복수회 반복하는 단계를 더 포함하는 것을 특징으로 하는 박막 형성 방법.
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