KR102300403B1 - 박막 증착 방법 - Google Patents

박막 증착 방법 Download PDF

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KR102300403B1
KR102300403B1 KR1020140161825A KR20140161825A KR102300403B1 KR 102300403 B1 KR102300403 B1 KR 102300403B1 KR 1020140161825 A KR1020140161825 A KR 1020140161825A KR 20140161825 A KR20140161825 A KR 20140161825A KR 102300403 B1 KR102300403 B1 KR 102300403B1
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time
precursor
supplying
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강동석
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에이에스엠 아이피 홀딩 비.브이.
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • 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
    • H01L21/02205—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 the layer being characterised by the precursor material for deposition
    • H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • 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
    • H01L21/02123—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 silicon
    • H01L21/02164—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 silicon the material being a silicon oxide, e.g. SiO2

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  • Formation Of Insulating Films (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

본 발명의 한 실시예에 따른 박막 증착 방법은 기판 위에 규소를 포함하는 보호층을 형성하는 단계, 그리고 상기 보호층 위에 희생층을 형성하는 단계를 포함하고, 상기 보호층과 상기 희생층은 규소(Si)를 포함하고, 상기 보호층을 형성하는 단계는 규소를 포함하는 전구체를 공급하는 단계와, 퍼지 기체를 활성화한 플라즈마를 공급하는 단계를 포함한다.

Description

박막 증착 방법 {METHOD OF DEPOSITING THIN FILM}
본 발명은 박막 증착 방법에 관한 것이다.
최근 반도체 증착 공정에서, 이산화 규소(SiO2) 막을 희생층(sacrificial layer)으로 이용하는 방법이 제시되었다. 특히, 이산화 규소(SiO2)로 이루어진 희생층은 반도체 공정 중 사진 공정에서 많이 이용된다.
그러나, 사진 공정에 이용되는 포토레지스트(PR; Photo Resist) 위에 이산화 규소(SiO2) 막을 증착할 때, 반응 기체인 산소 라디칼(oxygen radical)이 포토레지스트에 포함되어 있는 탄소(carbon) 및 수소(hydrogen)와 반응하여 포토레지스트가 수축되어 포토레지스트의 CD(Critical Dimension)가 변형되는 문제점이 있다.
본 발명이 해결하고자 하는 발명은 포토레지스트 위에 산화 규소막을 증착하더라도, 포토레지스트가 수축되는 것을 방지할 수 있는 박막 증착 방법을 제공하는 것이다.
본 발명의 한 실시예에 따른 박막 증착 방법은 기판 위에 규소를 포함하는 보호층을 형성하는 단계, 그리고 상기 보호층 위에 희생층을 형성하는 단계를 포함하고, 상기 보호층과 상기 희생층은 규소(Si)를 포함한다.
상기 보호층을 형성하는 단계는 제1 시간(t1), 제2 시간(t2), 제3 시간(t3) 그리고, 제4 시간(t4) 동안 퍼지 기체(purge gas)를 공급하는 단계, 제1 시간(t1) 동안 제1 전구체(precursor)를 공급하는 단계, 그리고 제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급하는 단계를 포함할 수 있다.
상기 보호층을 형성하는 단계는 제1 시간(t1), 제2 시간(t2), 제3 시간(t3) 그리고, 제4 시간(t4) 동안 퍼지 기체(purge gas)를 공급하는 단계, 제1 시간(t1), 제2 시간(t2), 제3 시간(t3) 그리고, 제4 시간(t4) 동안 제1 전구체(precursor)를 공급하는 단계, 그리고 제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급하는 단계를 포함할 수 있다.
상기 보호층을 형성하는 단계는 제1 시간(t1) 시간 동안 제1 전구체(precursor)를 공급하는 단계, 제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급하는 단계, 그리고 상기 제1 시간(t1)과 상기 제3 시간(t3) 사이의 제2 시간(t2) 시간 동안 기체 공급을 멈추는 단계를 포함할 수 있다.
상기 희생층을 형성하는 단계는 제5 시간(t5), 제6 시간(t6), 제7 시간(t7), 그리고 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하는 단계, 제5 시간(t5) 동안 제2 전구체(precursor)를 공급하는 단계, 제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하는 단계, 그리고 제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급하는 단계를 포함할 수 있다.
상기 제1 전구체와 상기 제2 전구체는 서로 같거나 서로 다를 수 있다.
상기 제1 전구체와 상기 제2 전구체는 규소(Si)를 포함하는 알콕시화물(alkoxide) 계열, 규소(Si)를 포함하는 아민(amine) 계열, 규소(Si)를 포함하는 아미노실란(aminosilane) 계열, 규소(Si)를 포함하는 염화물(chloride) 계열 중 적어도 어느 하나를 포함할 수 있다.
상기 제1 전구체와 상기 제2 전구체는 TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함하고, 상기 반응 기체는 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함할 수 있다.
상기 보호층을 형성하는 단계와 상기 희생층을 형성하는 단계는 하나의 반응기 내에서 인시투(in-situ)로 진행될 수도 있고 혹은 복수 개의 개별 반응기에서 별도로 진행(ex-situ)될 수도 있다.
본 발명의 실시예에 따른 박막 증착 방법에 따르면, 포토레지스트 위에 산화 규소막을 증착하더라도, 포토레지스트가 수축되는 것을 방지할 수 있다.
도 1은 본 발명의 한 실시예에 따른 박막 증착 방법의 기체 공급 주기를 도시한 도면이다.
도 2는 본 발명의 다른 한 실시예에 따른 박막 증착 방법의 기체 공급 주기를 도시한 도면이다.
도 3은 본 발명의 다른 한 실시예에 따른 박막 증착 방법의 기체 공급 주기를 도시한 도면이다.
도 4는 본 발명의 한 실험예의 결과를 나타내는 그래프이다.
도 5a 및 도 5b는 본 발명의 다른 한 실험예의 결과를 나타내는 그래프이다.
그러면 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.
도면에서 여러 층 및 영역을 명확하게 표현하기 위하여 두께를 확대하여 나타내었다. 명세서 전체를 통하여 유사한 부분에 대해서는 동일한 도면 부호를 붙였다. 층, 막, 영역, 판 등의 부분이 다른 부분 "위에" 있다고 할 때, 이는 다른 부분 "바로 위에" 있는 경우 뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 반대로 어떤 부분이 다른 부분 "바로 위에" 있다고 할 때에는 중간에 다른 부분이 없는 것을 뜻한다.
그러면 도면을 참고로 하여 본 발명의 실시예에 따른 박막 증착 방법에 대하여 설명한다.
도 1을 참고하여, 본 발명의 한 실시예에 따른 박막 증착 방법에 대하여 설명한다. 도 1은 본 발명의 한 실시예에 따른 박막 증착 방법의 기체 공급 주기를 도시한 도면이다.
도 1을 참고하면, 본 실시예에 따른 박막 증착 방법은 제1 기체 공급 주기(m cycle)와 제2 기체 공급 주기(n cycle)를 포함한다. 제1 기체 공급 주기(m cycle)는 기판 위에 보호층을 형성하는 단계이고, 제2 기체 공급 주기(n cycle)는 희생층을 형성하는 단계이다.
제1 기체 공급 주기(m cycle) 동안, 제1 시간(t1) 내지 제4 시간(t4) 동안 퍼지 기체(purge gas)를 공급하면서, 제1 시간(t1) 동안 제1 전구체(precursor)를 공급하고, 제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급한다.
제1 시간(t1) 동안 반응 공간에 공급된 제1 전구체는 제3 시간(t3) 동안 제1 플라즈마가 공급되면서, 기판 위에 코팅되어, 보호층이 형성된다.
기판 위에 포토레지스트가 이미 형성된 후에, 제1 기체 공급 주기(m cycle)를 적어도 1회 이상 반복하면, 포토레지스트 위에 제1 전구체 층이 코팅(coating)되어 보호층이 형성된다. 제1 기체 공급 주기(m cycle) 동안, 제1 전구체 공급과 제1 플라즈마 공급이 교대로 반복될 수 있다.
포토레지스트 위에 원하는 두께를 가지는 보호층이 코팅된 후에, 제2 기체 공급 주기(n cycle)를 반복한다.
제2 기체 공급 주기(n cycle) 동안, 제5 시간(t5) 내지 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하면서, 제5 시간(t5) 동안 제2 전구체(precursor)를 공급하고, 제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하면서, 제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급한다.
제5 시간(t5) 동안 공급된 제2 전구체는 코팅되어 있는 보호층 위에 흡착되고, 공급되는 반응 기체는 제7 시간(t7) 동안 공급되는 제2 플라즈마에 의하여 활성화되어, 흡착된 제2 전구체와 반응하여, 원하는 박막을 형성한다.
제2 기체 공급 주기(n cycle)를 원하는 두께의 박막 층이 형성될 때까지 반복함으로써, 원하는 두께의 박막을 증착할 수 있다.
전구체는 규소(Si)를 포함한다. 보다 구체적으로, 규소(Si)를 포함하는 알콕시화물(alkoxide) 계열, 아민(amine) 계열, 아미노실란(aminosilane) 계열, 염화물(chloride) 계열 중 적어도 어느 하나를 포함할 수 있다. 예를 들면, TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함할 수 있다.
반응 기체는 산소를 포함할 수 있고, 보다 구체적으로, 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함할 수 있다.
제1 기체 공급 주기(m cycle) 동안 공급되는 제1 전구체와 제2 기체 공급 주기(n cycle) 동안 공급되는 제2 전구체는 서로 같을 수도 있고, 다를 수도 있다.
이처럼, 본 발명의 실시예에 따른 박막 증착 방법은 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle) 전에 포토레지스트 위에 원하는 두께를 가지는 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)를 포함함으로써, 제2 기체 공급 주기(n cycle) 동안 공급되는 반응 기체는 포토레지스트와 반응하지 않게 된다. 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle) 동안, 반응 기체 없이 소스 기체를 공급하여 코팅한다. 보다 구체적으로, 전구체를 반응기로 도입한 후, 퍼지기체, 예를 들어 아르곤(Ar)을 활성화시킨 아르곤 플라즈마(Ar plasma)를 공급하여, 포토레지스트 위에 소스 기체를 코팅한다. 이처럼, 반응 기체를 유입하지 않으면서 보호막을 형성하기 때문에, 포토레지스트의 구성 물질인 탄소와 수소가 손상되지 않고, 그대로 포토레지스트 내에 남게 되므로, 포토레지스트의 변형 혹은 수축이 일어나는 것을 방지할 수 있다.
포토레지스트 위에 원하는 두께를 가지는 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)와 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle)를 하나의 반응기 내에서 인시투(in-situ)로 진행할 수 있고, 이와는 달리 복수 개의 반응기에서 개별적으로 형성하는 액스 시투(ex-situ)로 진행할 수도 있다. 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)와 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle)를 하나의 반응기 내에서 인시투(in-situ)로 진행하는 경우, 하나의 반응기 내에서 보호층 형성 및 희생층 형성이 진행되기 때문에, 막 증착 효율을 저하시키지 않으면서, 희생층 형성 전에 보호층을 형성할 수 있다.
그러면, 도 2를 참고하여, 본 발명의 다른 한 실시예에 따른 박막 증착 방법에 대하여 설명한다. 도 2는 본 발명의 다른 한 실시예에 따른 박막 증착 방법의 기체 공급 주기를 도시한 도면이다.
도 2를 참고하면, 본 실시예에 따른 박막 증착 방법은 제1 기체 공급 주기(m cycle)와 제2 기체 공급 주기(n cycle)를 포함한다. 제1 기체 공급 주기(m cycle)은 기판 위에 보호층을 코팅하는 단계이고, 제2 기체 공급 주기(n cycle)는 희생층을 형성하는 단계이다.
제1 기체 공급 주기(m cycle) 동안, 제1 시간(t1) 내지 제4 시간(t4) 동안 퍼지 기체(purge gas)와 제1 전구체(precursor)를 공급하고, 제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급한다.
제1 시간(t1) 내지 제4 시간(t4) 동안 반응 공간에 공급된 제1 전구체는 제3 시간(t3) 동안 제1 플라즈마가 공급되면서, 기판 위에 코팅되어, 보호층이 형성된다.
기판 위에 포토레지스트가 이미 형성된 후에, 제1 기체 공급 주기(m cycle)를 적어도 1회 이상 반복하면, 포토레지스트 위에 제1 전구체 층이 코팅(coating)되어 보호층이 형성 된다. 제1 기체 공급 주기(m cycle) 동안, 제1 전구체를 연속적으로 공급하면서, 제1 플라즈마를 단속적(intermittently)으로 공급하는 것을 반복할 수 있다.
포토레지스트 위에 원하는 두께를 가지는 보호층이 코팅된 후에, 제2 기체 공급 주기(n cycle)를 반복한다.
제2 기체 공급 주기(n cycle) 동안, 제5 시간(t5) 내지 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하면서, 제5 시간(t5) 동안 제2 전구체(precursor)를 공급하고, 제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하면서, 제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급한다.
제5 시간(t5) 동안 공급된 제2 전구체는 코팅되어 있는 보호층 위에 흡착되고, 공급되는 반응 기체는 제7 시간(t7) 동안 공급되는 제2 플라즈마에 의하여 활성화되어, 흡착된 제2 전구체와 반응하여, 원하는 박막을 형성한다.
제2 기체 공급 주기(n cycle)를 원하는 두께의 박막 층이 형성될 때까지 반복함으로써, 원하는 두께의 박막을 증착할 수 있다.
전구체는 규소(Si)를 함유한다. 보다 구체적으로, Si을 함유하는 알콕시화물(alkoxide) 계열, 아민(amine) 계열, 아미노실란(aminosilane) 계열, 염화물(chloride) 계열 중 적어도 어느 하나를 포함할 수 있다. 예를 들면, TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함할 수 있다.
소스 기체는 산소를 포함할 수 있고, 보다 구체적으로, 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함할 수 있다.
제1 기체 공급 주기(m cycle) 동안 공급되는 제1 전구체와 제2 기체 공급 주기(n cycle) 동안 공급되는 제2 전구체는 서로 같을 수도 있고, 다를 수도 있다.
이처럼, 본 발명의 실시예에 따른 박막 증착 방법은 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle) 전에 포토레지스트 위에 원하는 두께를 가지는 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)를 포함함으로써, 제2 기체 공급 주기(n cycle) 동안 공급되는 반응 기체는 포토레지스트와 반응하지 않게 된다. 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)동안, 반응 기체 없이 소스 기체를 공급하여 코팅한다. 보다 구체적으로, 전구체를 반응기로 도입한 후, 퍼지기체, 예를 들어 아르곤(Ar)을 활성화시킨 아르곤 플라즈마(Ar plasma)를 공급하여, 포토레지스트 위에 소스 기체를 코팅한다. 이처럼, 반응 기체를 유입하지 않으면서 보호막을 형성하기 때문에, 포토레지스트의 구성 물질인 탄소와 수소가 손상되지 않고, 그대로 포토레지스트 내에 남게 되므로, 포토레지스트의 변형 혹은 수축이 일어나는 것을 방지할 수 있다.
포토레지스트 위에 원하는 두께를 가지는 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)와 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle)를 하나의 반응기 내에서 인시투(in-situ)로 진행할 수 있고, 이와는 달리 복수 개의 반응기에서 개별적으로 형성하는 액스 시투(ex-situ)로 진행할 수도 있다.. 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)와 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle)를 하나의 반응기 내에서 인시투(in-situ)로 진행하는 경우, 하나의 반응기 내에서 보호층 형성 및 희생층 형성이 진행되기 때문에, 막 증착 효율 및 생산성을 저하시키지 않으면서, 희생층 형성 전에 보호층을 형성할 수 있다.
그러면, 도 3을 참고하여, 본 발명의 다른 한 실시예에 따른 박막 증착 방법에 대하여 설명한다. 도 3은 본 발명의 다른 한 실시예에 따른 박막 증착 방법의 기체 공급 주기를 도시한 도면이다.
도 3을 참고하면, 본 실시예에 따른 박막 증착 방법은 제1 기체 공급 주기(m cycle)와 제2 기체 공급 주기(n cycle)를 포함한다. 제1 기체 공급 주기(m cycle)은 기판 위에 보호층을 코팅하는 단계이고, 제2 기체 공급 주기(n cycle)는 희생층을 형성하는 단계이다.
제1 기체 공급 주기(m cycle) 동안, 제1 시간(t1) 동안 제1 전구체(precursor)를 공급하고, 제2 시간(t2) 동안 기체 공급 주기를 멈추고, 제3 시간(t3) 동안 퍼지 기체(purge gas)를 공급하면서, 제1 플라즈마(plasma)를 공급한다.
제1 시간(t1) 동안 반응 공간에 공급된 제1 전구체는 제3 시간(t3) 동안 제1 플라즈마가 공급되면서, 기판 위에 코팅되어, 보호층이 형성된다.
기판 위에 포토레지스트가 이미 형성된 후에, 제1 기체 공급 주기(m cycle)를 적어도 1회 이상 반복하면, 포토레지스트 위에 제1 전구체 층이 코팅(coating)되어 보호층이 형성 된다. 제1 기체 공급 주기(m cycle) 동안, 제1 전구체 공급과 제1 플라즈마 공급이 교대로 반복될 수 있다.
포토레지스트 위에 원하는 두께를 가지는 보호층이 코팅된 후에, 제2 기체 공급 주기(n cycle)를 반복한다.
제2 기체 공급 주기(n cycle) 동안, 제5 시간(t5) 내지 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하면서, 제5 시간(t5) 동안 제2 전구체(precursor)를 공급하고, 제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하면서, 제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급한다.
제5 시간(t5) 동안 공급된 제2 전구체는 코팅되어 있는 보호층 위에 흡착되고, 공급되는 반응 기체는 제7 시간(t7) 동안 공급되는 제2 플라즈마에 의하여 활성화되어, 흡착된 제2 전구체와 반응하여, 원하는 박막을 형성한다.
제2 기체 공급 주기(n cycle)를 원하는 두께의 박막 층이 형성될 때까지 반복함으로써, 원하는 두께의 박막을 증착할 수 있다.
전구체는 규소(Si)를 함유한다. 보다 구체적으로, Si을 함유하는 알콕시화물(alkoxide) 계열, 아민(amine) 계열, 아미노실란(aminosilane) 계열, 염화물(chloride) 계열 중 적어도 어느 하나를 포함할 수 있다. 예를 들면, TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함할 수 있다.
반응 기체는 산소를 포함할 수 있고, 보다 구체적으로, 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함할 수 있다.
제1 기체 공급 주기(m cycle) 동안 공급되는 제1 전구체와 제2 기체 공급 주기(n cycle) 동안 공급되는 제2 전구체는 서로 같을 수도 있고, 다를 수도 있다.
이처럼, 본 발명의 실시예에 따른 박막 증착 방법은 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle) 전에 포토레지스트 위에 원하는 두께를 가지는 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)를 포함함으로써, 제2 기체 공급 주기(n cycle) 동안 공급되는 반응 기체는 포토레지스트와 반응하지 않게 된다. 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)동안, 반응 기체 없이 소스 기체를 공급하여 코팅한다. 보다 구체적으로, 전구체를 반응기로 도입한 후, 퍼지기체, 예를 들어 아르곤(Ar)을 활성화시킨 아르곤 플라즈마(Ar plasma)를 공급하여, 포토레지스트 위에 소스 기체를 코팅한다. 이처럼, 반응 기체를 유입하지 않으면서 보호막을 형성하기 때문에, 포토레지스트의 구성 물질인 탄소와 수소가 손상되지 않고, 그대로 포토레지스트 내에 남게 되므로, 포토레지스트의 변형 혹은 수축이 일어나는 것을 방지할 수 있다.
포토레지스트 위에 원하는 두께를 가지는 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)와 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle)를 하나의 반응기 내에서 인시투(in-situ)로 진행할 수 있고, 이와는 달리 복수 개의 반응기에서 개별적으로 형성하는 액스 시투(ex-situ)로 진행할 수도 있다. 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle)와 희생층과 같은 박막을 증착하기 위한 제2 기체 공급 주기(n cycle)를 하나의 반응기 내에서 인시투(in-situ)로 진행하는 경우, 하나의 반응기 내에서 보호층 형성 및 희생층 형성이 진행되기 때문에, 막 증착 효율 및 생산성을 저하시키지 않으면서, 희생층 형성 전에 보호층을 형성할 수 있다.
그러면, 도 4를 참고하여, 본 발명의 한 실험예의 결과에 대하여 설명한다. 본 실험예에서는 본 발명의 실시예에 따른 박막 증착 방법과 같이, 포토레지스트 위에 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle) 후에 제2 기체 공급 주기(n cycle)를 반복하여, 보호층과 희생층을 적층한 경우와, 기존의 박막 증착 방법과 같이, 포토레지스트 위에 희생층만 형성한 경우에 대하여, 포토레지스트의 수축을 측정하여, 그 결과를 도 4에 나타내었다.
도 4를 참고하면, 본 발명의 실시예에 따른 박막 증착 방법과 같이 포토레지스트 위에 보호층을 코팅한 후에, 희생층을 형성한 경우, 포토레지스트는 약 2Å 수축되었으나, 기존의 박막 증착 방법과 같이, 포토레지스트 위에 희생층만 형성한 경우, 포토레지스트는 약 50Å 수축되었다. 이처럼, 본 발명의 실시예에 따른 박막 증착 방법에 따르면, 포토레지스트 위에 규소를 포함하는 희생층을 적층하더라도, 포토레지스트의 수축 등의 변형 발생이 낮아짐을 알 수 있었다.
그러면, 도 5a 및 도 5b를 참고하여, 본 발명의 다른 한 실험예의 결과에 대하여 설명한다. 본 실험예에서는 본 발명의 실시예에 따른 박막 증착 방법과 같이, 포토레지스트 위에 보호층을 코팅하기 위한 제1 기체 공급 주기(m cycle) 후에 제2 기체 공급 주기(n cycle)를 반복하여, 보호층과 희생층을 적층한 경우의 막의 성분을 AES (Auger Electron Spectroscopy) 분석하여, 그 결과를 도 5a 및 도 5b에 나타내었다.
도 5a를 참고하면, 보호막을 증착하기 위한 제1 기체 공급 주기(m cycle) 동안에는 규소(Si) 막이 형성되었음을 알 수 있었고, 도 5b를 참고하면, 희생층을 형성하기 위한 제2 기체 공급 주기(n cycle) 동안에는 이산화규소(SiO2) 막이 형성됨을 알 수 있었다. 이처럼, 본 발명의 실시예에 따른 박막 증착 방법에 따르면, 규소를 포함하는 전구체를 공급하고, 아르곤과 같은 퍼지 기체 플라즈마를 공급하여, 반응 기체 없이, 규소를 포함하는 보호층을 형성할 수 있음을 알 수 있었다.
이처럼, 본 발명의 실시예에 따른 박막 증착 방법에 따르면, 포토레지스트 위에 규소로 이루어진 보호층을 형성한 후에, 그 위에 이산화규소층으로 이루어진 희생층을 형성함으로써, 희생층 형성 시 공급되는 반응 기체가 포토레지스트에 주는 영향을 줄일 수 있다. 이에 따라, 포토레지스트 위에 이산화규소와 같은 희생층을 적층하는 경우에도, 포토레지스트가 수축되는 것을 방지할 수 있다.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.

Claims (17)

  1. 포토레지스트를 포함하는 기판의 상기 포토레지스트 위에, 상기 포토레지스트의 수축을 방지하기 위하여, 규소를 포함하는 보호층을 형성하는 단계, 그리고
    상기 보호층 위에 희생층을 형성하는 단계를 포함하고,
    상기 보호층과 상기 희생층은 규소(Si)를 포함하고,
    상기 보호층을 형성하는 단계는 규소를 포함하는 전구체를 공급하는 단계와, 퍼지 기체를 활성화한 플라즈마를 공급하는 단계를 포함하는 박막 증착 방법.
  2. 제1항에서,
    상기 보호층을 형성하는 단계는
    제1 시간(t1), 제2 시간(t2), 제3 시간(t3) 그리고, 제4 시간(t4) 동안 퍼지 기체(purge gas)를 공급하는 단계,
    제1 시간(t1) 동안 제1 전구체(precursor)를 공급하는 단계, 그리고
    제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급하는 단계를 포함하는 박막 증착 방법.
  3. 제2항에서,
    상기 희생층을 형성하는 단계는
    제5 시간(t5), 제6 시간(t6), 제7 시간(t7), 그리고 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하는 단계,
    제5 시간(t5) 동안 제2 전구체(precursor)를 공급하는 단계,
    제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하는 단계, 그리고
    제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급하는 단계를 포함하는 박막 증착 방법.
  4. 제3항에서,
    상기 제1 전구체와 상기 제2 전구체는 서로 같거나 서로 다른 박막 증착 방법.
  5. 제4항에서,
    상기 제1 전구체와 상기 제2 전구체는 규소(Si)를 포함하는 알콕시화물(alkoxide) 계열, 규소(Si)를 포함하는 아민(amine) 계열, 규소(Si)를 포함하는 아미노실란(aminosilane) 계열, 규소(Si)를 포함하는 염화물(chloride) 계열 중 적어도 어느 하나를 포함하는 박막 증착 방법.
  6. 제5항에서,
    상기 제1 전구체와 상기 제2 전구체는 TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함하고,
    상기 반응 기체는 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함하는 박막 증착 방법.
  7. 제1항에서,
    상기 보호층을 형성하는 단계는
    제1 시간(t1), 제2 시간(t2), 제3 시간(t3) 그리고, 제4 시간(t4) 동안 퍼지 기체(purge gas)를 공급하는 단계,
    제1 시간(t1), 제2 시간(t2), 제3 시간(t3) 그리고, 제4 시간(t4) 동안 제1 전구체(precursor)를 공급하는 단계, 그리고
    제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급하는 단계를 포함하는 박막 증착 방법.
  8. 제7항에서,
    상기 희생층을 형성하는 단계는
    제5 시간(t5), 제6 시간(t6), 제7 시간(t7), 그리고 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하는 단계,
    제5 시간(t5) 동안 제2 전구체(precursor)를 공급하는 단계,
    제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하는 단계, 그리고
    제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급하는 단계를 포함하는 박막 증착 방법.
  9. 제8항에서,
    상기 제1 전구체와 상기 제2 전구체는 서로 같거나 서로 다른 박막 증착 방법.
  10. 제9항에서,
    상기 제1 전구체와 상기 제2 전구체는 규소(Si)를 포함하는 알콕시화물(alkoxide) 계열, 규소(Si)를 포함하는 아민(amine) 계열, 규소(Si)를 포함하는 아미노실란(aminosilane) 계열, 규소(Si)를 포함하는 염화물(chloride) 계열 중 적어도 어느 하나를 포함하는 박막 증착 방법.
  11. 제10항에서,
    상기 제1 전구체와 상기 제2 전구체는 TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함하고,
    상기 반응 기체는 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함하는 박막 증착 방법.
  12. 제1항에서,
    상기 보호층을 형성하는 단계는
    제1 시간(t1) 시간 동안 제1 전구체(precursor)를 공급하는 단계, 그리고
    제3 시간(t3) 동안 제1 플라즈마(plasma)를 공급하는 단계를 포함하는 박막 증착 방법.
  13. 제12항에서,
    상기 보호층을 형성하는 단계는
    상기 제1 시간(t1)과 상기 제3 시간(t3) 사이의 제2 시간(t2) 시간 동안 기체 공급을 멈추는 단계를 더 포함하는 박막 증착 방법.
  14. 제12항에서,
    상기 희생층을 형성하는 단계는
    제5 시간(t5), 제6 시간(t6), 제7 시간(t7), 그리고 제8 시간(t8) 동안 퍼지 기체(purge gas)를 공급하는 단계,
    제5 시간(t5) 동안 제2 전구체(precursor)를 공급하는 단계,
    제5 시간(t5) 내지 제8 시간(t8) 동안 반응 기체(reactant gas)를 공급하는 단계, 그리고
    제7 시간(t7) 동안 제2 플라즈마(plasma)를 공급하는 단계를 포함하는 박막 증착 방법.
  15. 제14항에서,
    상기 제1 전구체와 상기 제2 전구체는 서로 같거나 서로 다른 박막 증착 방법.
  16. 제15항에서,
    상기 제1 전구체와 상기 제2 전구체는 규소(Si)를 포함하는 알콕시화물(alkoxide) 계열, 규소(Si)를 포함하는 아민(amine) 계열, 규소(Si)를 포함하는 아미노실란(aminosilane) 계열, 규소(Si)를 포함하는 염화물(chloride) 계열 중 적어도 어느 하나를 포함하는 박막 증착 방법.
  17. 제16항에서,
    상기 제1 전구체와 상기 제2 전구체는 TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DIPAS, SiH3N(iPr)2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; DCS, SiH2Cl2; 3DMAS, SiH(N(Me)2)3; BEMAS, Si H2[N(Et)(Me)]2; AHEAD, Si2 (NHEt)6; TEAS, Si(NHEt)4; Si3H8 중 적어도 하나를 포함하고,
    상기 반응 기체는 산소(O2), 오존(O3), 아산화질소(N2O), 일산화 질소(NO) 중 적어도 하나를 포함하는 박막 증착 방법.
KR1020140161825A 2014-11-19 2014-11-19 박막 증착 방법 KR102300403B1 (ko)

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