KR20010024652A - 유기 박막의 저압 증기상 증착 - Google Patents

유기 박막의 저압 증기상 증착 Download PDF

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KR20010024652A
KR20010024652A KR1020007005399A KR20007005399A KR20010024652A KR 20010024652 A KR20010024652 A KR 20010024652A KR 1020007005399 A KR1020007005399 A KR 1020007005399A KR 20007005399 A KR20007005399 A KR 20007005399A KR 20010024652 A KR20010024652 A KR 20010024652A
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organic
reaction chamber
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precursor
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스테판 알. 포레스트
폴 버로우즈
블라디미르 에스. 반
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엘렌 제이. 시니스갈리
더 트러스티즈 오브 프린스턴 유니버시티
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Abstract

본 발명은 기판(58)상에 유기 박막을 형성시키기 위한 방법에 관한 것으로서, 상기 방법은 기상에서 다수의 유기 프리커서(precursor)(14,48)를 제공하고, 대기보다 낮은 압력에서 다수의 유기 프리커서(14,48)를 반응시키는 단계를 포함한다. 또한 상기 방법으로 형성되는 박막 및 상기 방법을 수행하도록 사용되는 장치가 포함된다. 상기 방법은 유기 발광 장치의 형성 및 기타 디스플레이-관련 기술에 적합하다.

Description

유기 박막의 저압 증기상 증착 {LOW PRESSURE VAPOR PHASE DEPOSITION OF ORGANIC THIN FILMS}
정부 권리
본 발명은, 미국 공군 OSR(과학 연구국(Office of Scientific Research))에 의해 제정된, 계약 번호 제 F49620-92-J-05 24 호(프린스턴 대학교(Princeton University))하에서 정부 지원으로 이루어졌다. 정부는 본 발명의 일정한 권리를 갖는다.
유기 전장발광(electroluminescence) 분야는 급속도로 성장중인 기술이다. 디스플레이에 대한 잠재적인 적용에 의해 향상되는, 유기 발광 장치(OLEDs)는 3% 이상의 외부 양자 효율, 및 비디오 밝기로 10,000 시간의 작동 수명을 달성할 수 있다. 작은 분자 및 폴리머(polymer)-계 OLEDs 모두 공지되어 있으나, 폴리머-계 장치는 스핀-온(spin-on) 증착 기법에 의해 단순하고 저렴한 제조에 관한 일반적 장점을 갖는다. 반대로, 작은 분자 장치는, 스핀-온 증착보다 통상적으로 더 고가의 공정인, 진공에서 열 증발에 의해 통상적으로 제조된다. OLED 구조체 및 공정 기술의 실시예가, 참조로 본문에 도입되는, 공개된 PCT 출원 제 WO 96/19792 호에 제공된다.
유기 기상 증착(OVPD)의 이용은 저가를 지향하여, 디스플레이와 같은 다수의 잠재적 광자 장치 적용을 지니는 작은 분자량 유기층의 대규모 증착을 진행시켰다. OVPD 공정은, 각각이 참조로 본문에 도입되는, Forrest et al.의 미국 특허 번호 제 5,554,220 호; S.R. Forrest et al.의 "Intense Second Harmonic Generation and Long-Range Structural Ordering in Thin Films of an Organic Salt Grown by Organic Vapor Phase Deposition", 68 Appl. Phys. Lett. 1326 (1996); 및 P.E. Burrows et al.의 "Organic Vapor Phase Deposition: a New Method for the Growth of Organic Thin Films with Large Optical Non-linearities", 156 J. of Crystal Growth 91 (1995)에 게시된다.
OVPD 공정은, 가스가 바람직한 박막을 형성하도록 응축되는, 기판으로 원 물질을 운반하는 캐리어(carrier) 가스를 사용한다. OVPD 기술은, 예를 들면, 가열된 기판으로 캐리어 가스에 의해 운반되는, 휘발성 프리커서 4'-디메틸라미노(dimethylamino)-N-메틸(methyl)-4-스틸바졸리움(stilbazolium) 요오드화물 (DASI) 및 메틸 p-톨루엔설퍼네이트(toluensulfonate) (메틸토실레이트(methyltosylate), MT)로부터, 광학적으로 비선형 유기 (NLO) 염분, 4'-디메틸라미노-N-메틸-4-스틸바졸리움 토실레이트(tosylate) (DAST)의 막을 증착시키도록 사용되었다. 이러한 공정에서, DASI는 4-디메틸라미노-4-스틸바졸(stilbazole) (DAS)을 형성하도록 열분해되고, 이어서 기판상에 DAST를 형성하도록 MT와 반응한다.
근본적으로 다른 증기압을 갖는 물질들의 제어되는 공통-증착에 대한 능력때문에, OVPD는 다중-조성 박막의 정확한 화학량론적 성장을 위한 유일한 방법인 것이 인지된다. 그러나, OVPD 공정은 대기압에서 수행되고, 대기압에서 또는 그 부근에서 성장된 막은 기상 응집 및 방산이 한정된 성장 공정에 기인하여 종종 거칠고 불균일한 표면 조직을 갖는다.
발명의 요약
본 발명은 우수한 표면 특성을 가지는 유기 박막을 제조하는 저압 증착 기술을 이용한다. 한가지 관점에서, 본 발명은 기판상에 유기 박막을 형성시키기 위한 방법을 포함하는데, 상기 방법은, 기상에 있는, 다수의 유기 프리커서를 제공하고; 기판상에 박막을 형성하도록 기판이 존재할 경우 대기압보다 낮은 압력에서 다수의 유기 프리커서를 반응시키는 단계를 포함한다. 다른 관점에서, 본 발명은 상기 방법에 의해 형성되는 유기 막을 포함한다. 또 다른 관점에서, 본 발명은 기판상에 유기 막을 형성시키기 위해 대기압보다 낮은 압력에서 유기 프리커서의 반응을 용이하게 하도록 설계된 장치를 포함한다.
본 발명의 한가지 장점은 상기 막에서 각 구성 요소의 양이 정확하고 정밀하게 제어될 수 있는 다중-조성 유기 박막을 본 발명이 제공한다는 것이다.
본 발명의 다른 장점은 본 발명이 매끄러운 표면을 가지는 균일한 유기 박막을 제공하는 것이다.
본 발명의 다른 장점은 본 발명이 저압 유기 기상 증착법 및 유기 발광 물질 및 광학적으로 비선형 유기 염분의 박막의 성장을 위한 장치를 제공하는 것이다.
본 발명의 다른 장점은 본 발명이 저압 유기 분자선 증착법 및 유기 발광 물질 및 광학적으로 비선형 유기 염분의 박막의 형성을 위한 장치를 제공하는 것이다.
본 발명의 또다른 장점은 본 발명이 큰 기판 영역상에 유기 물질의 균일한 증착을 위한 방법 및 장치를 제공하는 것이다.
도면의 간단한 설명
도 1은, 본 발명의 실시예에 따른, LPOVPD 반응기,
도 2는, 본 발명의 실시예에 따른, OMVD 반응기,
도 3은, 본 발명의 실시예에 따른, 기판상으로 유기 물질의 연속 저압 증착을 위한 장치,
도 4A 및 도 4B는, 본 발명의 실시예에 따른, 반응 가스 디스트리뷰터(distributor)의, 각각의, 평면 및 단면도,
도 5는, 본 발명의 실시예에 따른, 롤-투-롤(roll-to-roll) 기판 이송 장치의 측면도.
본 발명은 광학 특성 박막의 제조에 관한 것이고, 좀더 상세하게는 비선형 광학 장치 및 유기 발광 장치에 적용하기 위한 상기 박막의 저압 제조에 관한 것이다.
본 발명은 대기압보다 낮은 압력하에서 기판상에 유기 박막을 성장시키기 위한 방법 및 장치를 제공한다. 본 발명의 방법은 본문에서 저압 유기 증기 증착(LPOVPD)으로 인지된다. 본 발명의 LPOVPD법은 다중-조성 유기 박막의 증착이 정밀하고 정확하게 제어되게 한다. 부가로, 본 발명의 박막은 낮은 표면 거칠기와 같은 우수한 표면 성질의 특징을 갖는다.
본 발명의 실시예에 따른 LPOVPD 반응기(10)는 도 1에 개략적으로 도시된다. 반응기(10)는, 반응 튜브(12)와 같은, 반응 챔버(chamber) 및 반응 챔버로 연장되는 배관을 포함한다. 반응 튜브(12)는, 예를 들면, 실험용 장치에서 10 cm의 직경 및 약 45 cm의 길이와 같은 적절한 치수를 가지는 실린더이다. 반응 튜브(12)는 유리 또는 석영과 같은 소정의 적합한 물질로 이루어진다. 도가니(14)와 같은 개방 콘테이너는 제 1 유기 프리커서 물질을 포함하고 반응 튜브(12)의 일단(20) 부근의 튜브(36)내에 위치된다. 이와는 달리, 도가니(14)는 반응 튜브(12)에 직접 또는 상기 반응 튜브내 선반이나 튜브에 위치된다. 도가니(14)는, 실질적으로 반응 튜브(12)를 둘러싸는, 멀티-존(multi-zone) 가열/냉각기(18)에 의해 가열 또는 냉각된다. 도가니(14)의 온도 제어는 도가니 (14)내에서 제 1 유기 프리커서 물질이 열분해 또는 휘발되게 한다. 불활성 캐리어 가스(carrier gas)의 조절된 유동(30)은 튜브(36)를 통해서 반응 챔버로 유동함으로써, 제 1 유기 프리커서의 증기가 반응 튜브(12)를 따라 상기 반응 튜브의 배출 단부(22)를 향해 유동하게 한다. 불활성 캐리어 가스는 질소, 헬륨, 아르곤, 크립톤(krypton), 크세논(xenon), 네온(neon) 등과 같은 불활성 가스이다. 수소, 암모니아 및 메탄과 같은, 감소하는 특성을 지니는 가스도 많은 유기 물질에 대해 불활성이다. 이들 감소 가스의 사용은 종종 바람직하지 않은 잉여 반응물의 연소를 지원하는 부가적 이점을 갖는다.
불활성 가스는 탱크(24)로부터 조절 밸브(26)를 통과하고 적어도 2개의 유동 경로(30 및 38)를 통해 전달되기 위한 배관(28)으로 그리고 반응 튜브(12)로 전달된다. 하나의 유동 경로(30)는 일련의 연결된 압력 조절기(32), 유동 미터(meter)(34) 및 캐리어 가스가 반응 튜브(12)의 단부(20)로 전달되는 급속 변환 밸브(35)를 포함한다. 제 2 유동 경로(38)는 일련의 연결된 압력 조절기(40), 유동 미터(42) 및, 제 2 유기 프리커서 물질(48)을 포함하는, 거품 발생기(46)로 캐리어 가스가 유동하는 급속 변환 밸브(39)를 포함한다. 제 2 유기 프리커서 물질(48)의 온도 제어를 용이하게 하도록, 거품 발생기(46)는 컨테이너(52)내의 용액기(50)에 부분적으로 침지된다. 탱크(24)로부터의 불활성 가스는 제 2 유기 프리커서(48)를 통해 그리고 반응 튜브(12)로 제 2 유기 프리커서(48)의 증기를 전달하는 배관(54)을 통해 기포화된다. 이러한 공정중에, 튜브(54)는 제 2 유기 프리커서가 거품 발생기로부터 반응기로 유동함에 따라 휘발된 제 2 유기 프리커서(48)의 재응축을 회피시키도록 효과적으로 고온에서 유지되어야 한다.
반응 튜브(12)로 유입되는 소정 프리커서의 양은 캐리어 가스의 온도 및 유동비와 반응물의 온도와 같은 변수를 조작함으로써 제어된다. LPOVPD법은 압력 질량 유동 제어기를 사용하는 프리커서 또는 반응물의 증기압이나 화학적 특성과 관계없이 프리커서나 반응물의 정확한 측정을 제공한다. 따라서 본 방법은 바람직한 막의 형성을 위해 필요한 비율이 폭넓게 다른 특성을 지니는 물질들이 결합되게 한다.
프리커서 유동은 급속 변환 밸브(35 및 39)를 사용함으로써 거의 순간적으로 연속되고 단속될 수 있다. 이들 밸브는, 소정의 주어진 시간에, 다른 프리커서 유동이 다른 조성물 및 특성의 막의 증착을 위해 반응기(12)로 유입될 수 있도록, 반응기(12)로 또는 바이-패스 라인(by-pass line)(도시 안됨)으로 프리커서 유동을 유도한다. 또한 밸브(39)는 거품 발생기(46)로 캐리어 가스의 유입을 조절한다. 따라서 밸브(35 및 39)는, 성장되는 막의 성질 및 조성을 변화시키기 위해, 반응기(12)로 유입되는 반응물 유동이 급격히 변화하게 한다. 따라서, 각각의 문자가 다른 분자층 또는 조성물을 나타내는, 예를 들면, ABAB, ABCABC, ABABCAB, 및 ABCDABCD-형 막을 성장시키는 것이 가능하다.
진공 펌프(66) 및 제어 스로틀 밸브(throttle valve)(68)는 배출부(62)에서 반응기(10)에 부착된다. 기판(58)상에 증착되지 않은 대부분의 유기 증기는 펌프(66)로부터 상류에 위치되는 트랩(trap)(64)에서 응축된다. 트랩(64)은, 예를 들면, 액화 질소 또는 중성의, 플루오르화 탄소유(fluorocarbon oil)를 포함한다. 스로틀 밸브(68)는 반응기(10)에서 압력을 조절한다. 적절한 압력 게이지가 반응기에서 바람직한 압력을 유지시키도록 제어 스로틀 밸브(68)로의 전기적 피드백(feedback)을 지니고 반응기에 연결된다(도시 안됨).
진공 펌프(66)는 반응 튜브(12)에 약 0.001 - 100 Torr의 압력을 제공한다. 수용체, 도너(donor), 및 단일 조성층의 소정 결합을 위한 실제 압력은 프리커서 물질을 휘발시키기 위해 요구되는 온도, 프리커서 물질의 응축을 방지하는 벽체 온도, 및 반응 영역 온도 구배에 관하여 실험적으로 결정된다. 압력에 관한 최적 선택은 각각의 증착된 유기층의 요건에 대해 유일하다. 예를 들면, 트리스(tris)-(8-하이드록시퀴놀린(hydroxyquinoline)) 알루미늄 (Alq3) 또는 N-N′-디페닐(diphenyl)-N,N-비스(bis)(3-메틸페닐(methylphenyl)) 1, 1′-바이페닐(biphenyl)-4,4′ 디아민(diamine)(TPD)과 같은 단일 조성층의 증착을 위한 최적 압력은 약 0.1 - 10 Torr이다.
본 발명의 박막이 증착되는 기판은 반도체 및 광학 제조에서 통상 볼 수 있는 물질들로부터 전형적으로 선택된다. 상기 물질은, 예를 들면, 유리, 석영, 실리콘, 갈륨(gallium) 비화물 및 기타 Ⅲ-Ⅴ 반도체, 알루미늄, 금 및 기타 귀금속 및 비귀금속, 폴리머 막, 실리콘 이산화물 및 실리콘 질화물, 인듐(indium)-주석-산화물 등을 포함한다. 고품질 광학 박막을 위해, 에피택시얼(epitaxial) 성장을 발생시키도록 증착되는 유기 막을 지니는 결정 상호작용을 제공하는 기판을 사용하는 것이 바람직하다. 상기 에피택시얼 성장을 이루도록, 증착되는 막과 유사한 결정 구조를 가지는 비극성 유기물로 기판을 코팅하는 것이 종종 요구된다.
부가로, 유기 박막이 기판(58)상에 증착됨에 따라, 기판의 온도를 제어하는 것이 종종 바람직하다. 기판 온도의 독립적 제어는, 예를 들면, 물, 가스, 프레온 글리세린(freon glycerin), 액화 질소 등과 같은 물질의 순환을 위해 온도-제어 블럭내에 채널(channel)을 가지는 온도-제어 블럭(60)과 기판(58)을 접촉시킴으로써 실행된다. 또한 그것은 블럭(60)상이나 그 부근에 위치되는 저항이나 복사 히터의 사용으로 가열될 수 있다.
도 1의 반응기(20)는 반응기(20)로 추가 프리커서를 공급하는 다중 거품 발생기(46N)를 포함하도록 확장가능하다. 이와 유사하게, 다중 캐리어 가스 유동 경로(30N)가 도가니(14N)로부터 역시 추가 프리커서를 반송하도록 사용된다. 대안으로서, 도가니(14,14N)는 추가 프리커서를 처리하기 위해 반응 튜브(12)내의 선반상이나 튜브에서 수직하게 적층될 수 있다. 증착되는 유기 막에 따라서, 하나 이상의 유동 경로(30,38)가 요구되는 프리커서 물질을 공급하도록 단독으로 또는 소정 결합을 이루어 사용된다.
본 발명의 방법은 증기 프리커서의 반응으로부터 폭넓게 다양한 유기 박막을 증착시키도록 사용된다. 본문에서 사용된 바와 같이, "반응"은 프리커서 반응물이 독특한 반응 생성물을 형성하는 화학 반응을 나타내고, 또는 이와는 달리, 그것은 단순히 프리커서 물질의 조합이나 혼합을 나타내며, 또는 프리커서 물질은 도너-수용체나 게스트-호스트(guest-host) 관계를 형성시킨다. 예를 들면, 본 발명에 따라, 다음의 NLO 물질은 표에 실린 프리커서의 반응에 의해 박막으로 형성된다:
막 물질 제 1 프리커서 제 2 프리커서
4′-디메틸라미노-N-메틸-4-스틸바졸리움 토실레이트(DAST) 4′-디메틸라미노-4-스틸바졸 (DAS) 메틸 토실레이트 (MT)
4′-디메틸라미노-4-메틸스틸바졸리움메탄설퍼네이트 (DASM) 메틸 메탄설퍼네이트 (MM) 4′-디메틸라미노-4-스틸바졸 (DAS)
4′-디메틸라미노-4-메틸스틸바졸리움트리플루오로메탄설퍼네이트 (DASMf) 메틸트리플루오로메탄설퍼네이트 (MfM) 4′-디메틸라미노-4-스틸바졸 (DAS)
4′-디메틸라미노-N-메틸-4-스틸바졸리움 토실레이트(DAST) 메틸 토실레이트 (MT) 4′-디메틸라미노-4-메틸스틸바졸리움다이오페녹사이드 (DASTh)
4′-메톡시-4-메틸스틸바졸리움 토실레이트(MeOST) 메틸 토실레이트 (MT) 4′-메톡시-4-메틸스틸바졸 (MeOS)
4′-디메틸라미노-N-메틸-4-스틸바졸리움 토실레이트(DAST) 메틸 토실레이트 (MT) 4′-디메틸라미노-4-에틸스틸바졸리움 요오드화물 (DAS(Et)I)
4′-디메틸라미노-N-메틸-4-스틸바졸리움 토실레이트(DAST) 메틸 토실레이트 (MT) 4′-디메틸라미노-4-에틸스틸바졸리움하이드록사이드 (DAS(Et)OH)
4′-디메틸라미노-4-아세틸스틸바졸리움 토실레이트(DAAST) 아세틸 톨루엔설퍼네이트 (AT) 4′-디메틸라미노-4-스틸바졸 (DAS)
4′ 디메틸라미노-4-메틸스틸바졸리움트리플루오로아세테이트(DASAf) 메틸 트리플루오로아세테이트(MAf) 4′-디메틸라미노-4-스틸바졸 (DAS)
OLEDs를 제조하는데 사용되는 발광 물질에 더욱 본질적으로 관련되는 다른 실시예에서, 프리커서는, 예를 들면, 테트라디스펄발렌(tetrathisferlvalene)(TFF) 및 7,7,8,8-테트라사이아노퀴노디메탄(tetracyanoquinodimethane)(TCNQ)으로 구성된다. 혼합 단계는 기판상에 증착되는 전하 전달 합성물 TTF-TCNQ를 결과적으로 발생시킨다. OLEDs에 관련되는 다른 실시예에서, 4-(디사이아노메틸렌(dicyanomethylene))-2-메틸-6-(p-디메틸라미노스티릴(dimethy-laminostyryl))-4H-피랜(pyran) (DCM)은 Alq3가 저유동비의 캐리어 가스 유동으로 첨가되는 동안 고유동비의 캐리어 가스 유동으로 첨가된다. 그 후 이들 유동은 중앙 반응 튜브에서 혼합됨으로써, 단일 발광층을 형성하도록 호스트 매트릭스(matrix) 막에서 게스트 분자의 바람직한 희석물을 제공한다. Alq3호스트에서 기타 게스트 분자의 예는 5,10,15,20-테트라페닐(tetraphenyl)-21H,23H-포르핀(porphine) (TPP), 루브렌(Rubrene), DCM2, 쿠마린(Coumarin) 등이다. 이에 대한 변화로서, 다중 도펀트(dopant)가 효과적인 폭넓은 색 변환을 얻도록 단일 호스트에 첨가될 수 있다.
다른 실시예에서, Alq3, 비스-(8-하이드록시퀴놀린) 알루미늄 옥시페닐(oxyphenyl) ((Alq2)′-OPh) 또는 이들 층의 도핑(doping)된 결합과 같은 발광층("EL")의 표면상에 층을 이룬, TPD;-4,4′-비스[N-(1-내프틸(naphthyl))-N-페닐-아미노] 바이페닐(biphenyl) (-NPD); 또는 MTDATA와 같은 홀(hole) 반송층("HTL")으로 구성되는 이중층 발광 장치는 바람직한 두께까지 HTL 및 EL을 연속하여 성장시킴으로써 성장된다. 이것은 유기물상에 추가층을 성장시키는 것, 또는 트리메틸(trimethyl)-인듐, 트리메틸-갈륨 등과 같은 유기 금속원을 사용하는 금속 접촉층상의 성장이 후속된다.
도 1에 관하여 게시된 장치 및 방법에 부가하여, 본 발명은 도 2에 도시된 바와 같은 저압 반응기(70) 및 방법을 포함한다. 반응기(70)는 변형된 초강력 진공 챔버(71) 및 밸브(72)에 연결되는 터보분자 펌프(도시 안됨)와 같은 진공 펌프를 포함한다. 챔버(71)에서 전형적인 챔버 기부(base) 압력은 10-3- 10-11Torr이다. 반응기(70)를 사용하여 유기층을 증착시키는 공정은 유기 분자선 증기 증착(OMVD)으로 호칭된다. LPOVPD 및 OMVD 모두 유기층의 증착을 위해 대기압보다 낮은 압력을 이용하지만, 이들 공정 사이의 주요 차이는 후자에서, 분자 평균 자유 경로는 챔버(70)의 치수와 유사하거나 그보다 더 크다는 것이다. 이와 비교하여, LPOVPD에서 평균 자유 경로는 가스 반응기 치수보다 현저하게 더 짧다. 따라서 OMVD는, 성장되는 막 두께, 순도 및 형태가 정확하게 동적 제어되도록, 인젝터(injector)로부터 기판으로 고도하게 유도된 분자"선"이 형성되게 한다.
거품 발생기(74)는 제 1 프리커서 물질(75)을 수용하기 위해 포함된다. 거품 발생기(74)는 컨테이너(76)에 위치되고 온도가 제어되는 배쓰(80)에 침지된다. 고순도 불활성 캐리어 가스(78)는 제 1 프리커서(75)를 통해 기포화되고, 가열된 배관(79)을 통과해서 인젝터(82)에 의해 진공 챔버(71)로 개별 증기를 운반한다. 챔버(71) 내부에서 일단, 프리커서 증기는 기판(85)상에 충돌하는 분자선(83)을 형성한다. 기판(85)에는, 예를 들면, 냉각제 포트(port)(81)와 같은 온도 제어를 제공하기 위한 수단이 제공된다.
진공 챔버(71)에는, 제 2 프리커서 물질(88)을 포함하는, 적어도 하나의 크누센(Knudsen) 또는 K-셀(cell)(86)이 임의로 제공된다. K-셀(86)은 진공하에서 증발제의 유출을 위해 균등하게 가열되고 제어되는 오븐이다. 예를 들면, K-셀(86)은 DASI 또는 기타 프리커서를 분류(cracking)시키도록 가열되고 결과로 발생되는 DAS를 승화시켜서, 상기 DAS는 분자선(89)으로서 반응기(70)로 분사된다. 이와는 달리, K-셀(86)은 Alq3와 같은 단일 조성물을 간단하게 승화시킨다. 이와는 달리, K-셀(86)은 열중성자화에 의해 가스 유동으로 승화되거나 증발되는 분자 종류의 농도를 희석시키는데 사용되는 캐리어 가스 입구를 지니고 장착된다. 이러한 희석 공정은 거품 발생기(74)로 캐리어 가스(78)의 유동 뿐만 아니라 배쓰(80) 및 크누센 셀(86)의 온도를 제어함으로써 DCM-Alq3와 같은 게스트-호스트 시스템의 정확한 도핑 수준을 얻는데 특히 유용하다.
분자선(83 및 89)은 유기 박막을 증착시키도록 기판(85)상에 충돌되는데, 두께는 석영 결정체(93)에 의해 모니터된다. 샘플 홀더(holder)(90)는 프리커서 물질의 균등한 증착 및 반응이 확실해지도록 회전된다. 프리커서 물질의 증착은, 분자선(83 및 89)을 막도록 사용되는, 셔터(shutter)(87)에 의해 더 제어된다.
또한 반응기(70)는 재증발된 프리커서 물질을 위해 최소로 진공 챔버(71)의 압력 유지를 지원하는 냉각된 덮개(91)를 임의로 포함한다. 또한 포함되는 것이 바람직한 것은 프리커서 물질이 이동함으로써 서로 오염시키는 것을 방지하는 구획부(92)이다.
반응기(70)는, 급속 변환 밸브, 바이패스 라인 등과 같은, 도 1에 도시된 LPOVPD 반응기의 다수의 동일한 부속체로 구성된다. 반응기(70)에는 기판(85)상에 다중 프리커서 물질의 증착을 위해 다중 크누센 셀 및 거품 발생기가 장착될 수 있다. 또한 반응기(70)는 샘플 도입을 위해 "로드-로크(load-lock)"(94)를 포함함이 바람직하다. 로드-로크(94)는 도어(door)(95) 및 진공 펌프(96)를 포함하고, 챔버(71)의 압력을 절충시키지 않는 샘플의 변화를 제공한다.
도 1의 장치는, 도 3에 도시된 실시예에 의해 나타낸 바와 같이, 큰 면적의 기판상에 유기층의 연속적인 증착을 위해 임의로 변형된다. 도 3의 장치는 로딩(loading) 챔버(146), 유기층 증착 챔버(150 및 152), 접촉 증착 챔버(154), 및 언로드(unload) 챔버(156)와 같은 다수의 진공 챔버를 포함한다. 실시예와 같이, 각각의 증착 챔버는 도 1의 LPOVPD 반응기(10)이다. 기판(137)은 각각의 챔버(150,152,154 및 156)를 통과하는 컨베이어 벨트(148)상에서 이송된다. 도 3에 도시된 실시예에서, 챔버(150,152 및 154)는 유기 증기의 응축을 방지하도록 복사 열원(158,160 및 162)을, 각각, 포함한다. 단지 2개의 유기층 증착 챔버(150 및 152)가 도 3에 도시되지만, 부가적 챔버가 바람직하다면 포함된다. 로딩 챔버(146)로부터 유기층 증착 챔버(150 및 152)로, 그리고 접촉 증착 챔버(154)로부터 언로드 챔버(156)로 통과시에, 기판(137)은 챔버(150,152, 및 154)에서 진공 상태를 절충시키지 않도록 에어 로크(도시 안됨)를 통해 통과한다. OLEDs에 관련되는 실시예로서, 챔버(150 및 152)는 TPD 및 Alq3,개별적으로 증착을 위해 사용되고 챔버(154)는 Mg:Ag 접촉층의 증착을 위해 사용된다.
도 3의 실시예에서 각각의 챔버(150,152, 및 154)는, 도 4A 및 4B에 상세하게 도시된 바와 같이, 유기 프리커서 물질의 증착을 위해 반응물 가스 분배기(RGD)(108)를 포함한다. RGD's(108)는 도 1 및 도 2의 유기 프리커서 반송 장치에 선택적으로 사용되고, 가스 커튼(120,120',120'' 및 120''')을 제공하도록 사용된다. RGD(108)는 다중 유기 프리커서가 증착되는 지점에서, 프리커서가 기판상에 증착될 때까지 분리 유지되어서, 프리커서의 반응이 확실하게 발생되게 한다. RGD(108)는 가열기(122), 제 2 캐리어 가스 입구(112) 및 가스 매니폴드(manifold)(132)를 포함한다. 가열기(122)는 유기 프리커서 물질의 너무 이른 응축을 방지한다. RGD(108)상에는 제 1 캐리어 가스 입구(114) 및 분배기 플레이트(plate)(110)가 존재한다. 제 1 캐리어 가스 입구(114)는, 예를 들면, MT와 같은 일반적으로 저휘발성의 제 1 유기 프리커서를 통상적으로 운반하는 가스를 공급한다. 제 1 캐리어 가스는, 예를 들면, 와이어 메쉬(wire mesh), 유리 필터 물질, 또는 다공성 스테인레스 강 플레이트인, 분배기 플레이트(110)를 통해 반응 챔버로 유입된다. 분배기 플레이트(110)를 통해 유동하는 캐리어 가스 기둥은 RGD(108)에 의해 보호된다. RGD(108)는, 예를 들면, DAS와 같은 일반적으로 저증기압의 제 2 유기 프리커서의 평면 가스 커튼(120)을 제공한다. 제 2 유기 프리커서를 포함하는 제 2 캐리어 가스는 입구(112)에서 유입되고 가스 매니폴드(132)로 유도된다. 매니폴드(132)는 매니폴드(132)를 둘러싸는, 환상 공동(126)으로 제 2 캐리어 가스를 공급하기 위한 홀(134)의 라인을 가지는 중공 튜브이다. 제 2 캐리어 가스는 슬릿(slit)(136)을 통해 RGD(108)에서 유출됨으로써, 상기 가스에 평면 커튼 형태를 부여한다.
실시예로서, 커튼(120)은 TPD 증기로 구성되고, 커튼(120')은 Alq3증기로 구성되며 커튼(120'')은 폴리피롤(polypyrole) 또는 전도성 표면을 형성하는 금속유기 화합물과 같은 증기로 구성된다. 바람직하다면, OLED에 의해 발산되는 빛 색깔의 제어나 조절은 도펀트 증기의 커튼(120''')을 형성하는 챔버(152)에서 부가적 RGD 장치(108)를 지니는 Alq3층의 적절한 도핑에 의해 영향받을 수 있다.
도 1, 도 2 또는 도 3의 장치는, 도 5에 도시된 바와 같은, "롤-투-롤" 기판 이송 시스템을 사용함으로써 임의로 변형된다. 도 5에 도시된 이송 시스템은 넓은 면적의, 가요성 기판상에 유기 박막의 증착을 위해 적합하다. 기판(180)은, 예를 들면, 폴리머 시트(sheet) 또는 금속박으로 이루어지고 롤(181)로부터 롤(182)로 이송된다. 기판(180)상으로 유기 프리커서의 증착은 기판(180)이 롤(181)로부터 전개되어 도 1의 반응 챔버에 노출되는 경우, 또는 도 2 및 도 3, 각각의 분자선이나 커튼에 노출되는 경우 발생된다. 롤(181 및 182)은, 가변 속도 모터와 같은, 소정의 적절한 수단에 의해 작동된다. 기판(180)이 롤(181)로부터 롤(182)로 통과하는 속도는 기판(180)상에 형성되는 유기 막의 두께를 나타낸다.
본 발명은 다음의 비-제한적 실시예와 관련하여 더 기술된다.
실시예 1
도 1의 장치를 이용해서, 유기 발광 물질의 층은 인듐 주석 산화물(ITO)의 투명 층으로 예비코팅(precoating)된 유리와 가요성 폴리에스터 기판들을 이용하여 성장되었다. ITO는 유리와 폴리에스터 기판들에 대하여 각각 1700Å과 1200Å의 두께를 가지는 장치의 애노드(anode)를 형성하여, 10 Ω과 60 Ω의 애노드 저항을 각각 산출한다. 유리 기판들은 초음파 배쓰에서 세제와 이온 제거수(deionized water)의 용액에서 헹구어짐으로써 세척되고, 그 후 1,1,1-트리클로로에탄에서 비등되고, 아세톤에서 헹궈지며, 최종적으로 2-프로판올에서 헹궈져서 세척되었다. 유기 용매에 노출되므로 손상을 피하기 위하여, 가요성 기판들은 단지 세제와 2-프로파놀 용액에서 헹구어짐으로써 세척되었다.
유리 기판들은 온도가 대략 220℃인 지점에서 반응 튜브(12)내에 위치되었다. ITO 표면에 증착된 제 1 층은 TPD, 정공 운반 물질이었다. 특히, TPD 증기는 도가니(14)로부터 질소 운반 가스를 통해 기판에 운반되었다. TPD 성장 조건들은 200 ±5℃ 원천 온도, 100 sccm 의 질소 캐리어 가스 유동비, 0.5 Torr의 반응기 압력 및 20분의 성장 시간이 포함되었다. 100 sccm 의 질소 유동비에서, 시스템의 레이놀즈 수(Reynolds number)는 ~500이였고, 층류 영역내에서 적절하게 작동됨을 나타낸다. TPD층은 100 - 300Å의 두께로 성장되었다.
증착후에, TPD 도가니 근처의 온도는 감소되고, 상응하는 질소 유동은 차단되었다. 다음에, Alq3의 전계 반송층은 Alq3증기를 도가니(14N)로부터 챔버(12) 내부로 운반하도록 각 질소 라인을 개방시킴으로써 성장되었다. Alq3성장 조건들은 247 ±8℃ 원천 온도, 50 sccm의 질소 유동비, 0.65 Torr의 압력, 및 10분의 성장 시간을 포함하였다. TPD와 Alq3양자의 증착 동안에, 기판은 스테인레스 강 기판 홀더로 냉각된 물을 이용하여 15℃로 유지되었다. TPD층은 700 - 1100Å 사이의 두께로 성장되었다.
Alq3층의 증착 후에, 기판은 반응기로부터 제거되고, Mg:Ag 상부 접촉은 열 증발에 의해 적용되었다. 접촉은 1000Å 두께의 보호 Ag층의 증발로 완성되었다.
증착동안 저압의 이용은 유기 층들이 평탄하고 균일한 표면을 가지도록 하였다. 예를 들면, TPD와 Alq3층들은 6 - 8Å과 9 - 11Å의 RMS 거칠기를 갖는 원자력 현미경 검사에 의하여 각각 측정되었다. 결과로 발생되는 OLED 장치들은 저전압에서 I∝V 이고 고전압에서 I∝V3인 전류-전압 특성을 나타내었다. V에 따른 I의 전력 법칙이 변화되는 턴-온(turn-on) 전압(VT)은 약 6V 였다.
실시예 2
NLO 막은 도 1에 도시된 장치를 이용하여 제공되었다. MT(48)는 30cm3거품 발생기 내부로 로딩되고, 그것의 온도는 실리콘 오일 배쓰(50)에서 약 80 - 100℃로 유지되었다. 질소 가스는 MT(48)를 통해서 거품을 발생시키기 위해 사용되어, MT 증기를 유리 튜브(54)를 통해서 도가니(14)를 약 5 cm 지나서 위치한 반응 튜브(12)내로 운반하고, 포함된 그것은 반응 튜브(12)와 DASI의 바닥에 위치되었다. 반응 튜브(12)내에서의 압력은 약 10-2Torr로 유지되었다. DAS 증기는 MT 증기와 반응해서 기판(58)상에 DAST의 고체 막을 형성하였고, 그것은 기판 블록(60)상에 유지되었다. 잉여 미반응 MT 증기와 특정 휘발성 부-반응 생성물은 배출 관(62)에서 배출되었다. 이렇게 형성된 DAST 막들은 예를 들면 광학 스위치로 유용하다.
본 발명은 우수한 표면 특성과 정확하고 정밀한 구성물을 구비한 유기 박막을 생산하기 위한 저압 증착 기술의 이용을 안출한다. 비록 본 발명의 다양한 실시예들이 본문에 게시되었지만, 당업자는 이 실시예들로부터 특정 변형들을 인지할 수 있으며, 이 변형들이 첨부된 청구항의 사상과 범위에 포함되는 것을 의미한다.
본문에 기술된 본 발명은 다음의 동시-계류중인 출원과 관련하여 이용될 수 있다: "ㅗㅗHigh Reliability, High Efficiency, Integratable Organic Light Emitting Devices and Methods of Producing Same", 일련 번호 제 08/774,119 호 (1996년, 12월 23일 출원); "Novel Materials for Multicolor LED's", 일련 번호 제 08/850,264 호 (1997년 5월 2일 출원); "Electron Transporting and Light Emitting Layers Based on Organic Free Radicals", 일련 번호 제 08/774,120 호 (1996년 12월 23일 출원); "Multicolor Display Devices", 일련 번호 제 08/772,333 호 (1996년 12월 23일 출원); "Red-Emitting Organic Light Emitting Devices (LED's)", 일련 번호 제 08/774,087 호 (1996년 12월 23일 출원); "Driving Circuit For Stacked Organic Light Emitting Devices", 일련 번호 제 08/792,050 호 (1997년 2월 3일 출원); "High Efficiency Organic Light Emitting Device Structures", 일련 번호 제 08/772,332 호 (1996년 12월 23일 출원); "Vacuum Deposited, Non-Polymeric Flexible Organic Light Emitting Devices", 일련 번호 제 08/789,319 호 (1997년 1월 23일 출원); "Displays Having Mesa Pixel Configuration", 일련 번호 제 08/794,595 호 (1997년 2월 3일 출원); "Stacked Organic Light Emitting Devices", 일련 번호 제 08/792,046 호 (1997년 2월 3일 출원); "High Contrast Transparent Organic Light Emitting Device Display", 일련 번호 제 08/821,380 호 (1997년 3월 20일 출원); "Organic Light Emitting Devices Containing A Metal Complex of 5-Hydroxy-Quinoxaline as A Host Material", 일련 번호 제 08/838,099 호 (1997년 4월 15일 출원); "Light Emitting Devices Having High Brightness", 일련 번호 제 08/844,353 호 (1997년 4월 18일 출원); "Organic Semiconductor Laser", 일련 번호 제 60/046,061 호 (1997년 5월 9일 출원); "Organic Semiconductor Laser", 일련 번호 제 08/859,468 호 (1997년 5월 19일 출원); "Saturated Full Color Stacked Organic Light Emitting Devices", 일련 번호 제 08/858,994 호 (1997년 5월 20일 출원); "An Organic Light Emitting Device Containing a Hole Injection Enhancement Layer", 일련 번호 제 08/865,491 호 (1997년 5월 29일 출원); "Plasma Treatment of Conductive Layers", 일련 번호 제 PCT/US97/10252 호 (1997년 6월 12일 출원); "Patterning of Thin Films for the Fabrication of Organic Multi-Color Displays", 일련 번호 제 PCT/US97/10289 호 (1997년 6월 12일 출원); "Double Heterostructure Infrared and Vertical Cavity Surface Emitting Organic Lasers", 일련 번호 제 60/053,176 호 (1997년 7월 18일 출원); "Oleds Containing Thermally Stable Asymmetric Charge Carrier Materials", 일련 번호 제 08/929,029 호 (1997년 9월 8일 출원), "Light Emitting Device with Stack of Oleds and Phosphor Downconverter", 일련 번호 제 08/925,403 호 (1997년 9월 9일 출원), "An Improved Method for Depositing Indium Tin Oxide Layers in Organic Light Emitting Devices", 일련 번호 제 08/928,800 호 (1997년 9월 12일 출원), "Azlactone-Related Dopants in the Emissive Layer of an Oled" (1997년 10월 9일 출원), 일련 번호 제 08/948,130 호, "A Highly Transparent Organic Light Emitting Device Employing A Non-Metallic Cathode", (1997년 11월 3일 출원), 변리사 서류 번호 제 10020/40 호 (가출원), 및 "A Highly Transparent Organic Light Emitting Device Employing a Non-Metallic Cathode", (1997년 11월 5일 출원), 변리사 서류 번호 제 10020/44 호, 각각의 동시-계류중인 출원은 상기 출원의 전체가 참조로 본문에 도입된다. 또한 본 발명은, 각각이 전체가 참조로 본문에 또한 도입되는, 각각의 동시-계류중인 미국 특허 출원 일련 번호 제 08/354,674 호, 제 08/613,207 호, 제 08/632,322 호 및 제 08/693,359 호와 가특허 출원 일련 번호 제 60/010,013 호, 제 60/024,001 호 및 제 60/025,501 호의 문제와 관련하여 이용될 수 있다.

Claims (43)

  1. 기판상에 유기 박막을 형성하는 방법에 있어서,
    증기 상인 다수의 유기 프리커서를 제공하는 단계; 및
    상기 다수의 유기 프로커서들을 기판상에서 대기보다 낮은 압력에서 반응시켜 상기 기판상에 상기 박막을 형성하는 단계
    를 포함하는 것을 특징으로 하는 방법.
  2. 제 1 항에 있어서, 상기 기판이 반응 챔버에 위치되는 것을 특징으로 하는 방법.
  3. 제 2 항에 있어서, 상기 다수의 유기 프로커서들중 하나를 상기 반응 단계전에 상기 반응 챔버내로 반송하는 단계를 더 포함하는 것을 특징으로 하는 방법.
  4. 제 3 항에 있어서, 상기 반송 단계는 상기 반송된 유기 프로커서를 상기 반응 챔버내로 운반하기 위해 불활성 가스를 사용하는 단계를 포함하는 것을 특징으로 하는 방법.
  5. 제 4 항에 있어서, 상기 불활성 가스가 질소, 아르곤, 헬륨, 네온, 크립톤, 및 크세논으로 이루어진 족으로부터 선택되는 것을 특징으로 하는 방법.
  6. 제 1 항에 있어서, 상기 다수의 유기 프로커서들중 적어도 하나가 MT, DASI, MM, MfM, DASTh, MeOSI, DAS(Et)I, DAS(Et)OH, 아세틸 톨루엔설포네이트, MAF, TTF, TCNQ, DCM, Alq3, TPP, TPD,-NPD, MTDATA, 및 (Alq2)'-OPh로 이루어진 족으로부터 선택되는 것을 특징으로 하는 방법.
  7. 제 3 항에 있어서, 상기 반송 단계전에 상기 반송된 유기 프로커서를 휘발시키는 단계를 더 포함하는 것을 특징으로 하는 방법.
  8. 제 7 항에 있어서,
    상기 휘발 단계가 상기 반송된 유기 프로커서를 거품발생기내로 로딩(loading)하는 단계를 포함하고;
    상기 반송 단계가 불활성 가스를 상기 거품발생기로 통과시켜 상기 반송된 유기 프로커서를 상기 반응 챔버내로 운반하는 단계를 포함하는 것을 특징으로 하는 방법.
  9. 제 7 항에 있어서,
    상기 휘발 단계가 상기 반송된 유기 프로커서를 개방 컨테이너내에 위치시키고, 상기 개방 컨테이너를 가열하는 단계들을 포함하고;
    상기 반송 단계가 불활성 가스를 상기 개방 컨테이너위로 통과시켜 상기 반송된 유기 프로커서를 상기 반응 챔버내로 운반하는 단계를 포함하는 것을 특징으로 하는 방법.
  10. 제 7 항에 있어서, 상기 휘발 단계가,
    상기 반송된 유기 프로커서를 상기 반응 챔버내부로 연장하는 크누센 셀(Knudsen cell)내부로 로딩시키는 단계; 및
    상기 크누센 셀을 가열하는 단계를 포함하는 것을 특징으로 하는 방법.
  11. 제 1 항에 있어서, 상기 기판이 회전 샘플 홀더에 장착되는 것을 특징으로 하는 방법.
  12. 제 1 항에 있어서, 상기 대기압보다 낮은 압력이 약 10-11에서 102Torr의 영역내에 있는 것을 특징으로 하는 방법.
  13. 제 1 항의 방법으로 제조된 유기 막.
  14. 제 13 항에 있어서, 상기 막이 발광 물질을 포함하는 것을 특징으로 하는 유기 막.
  15. 제 13 항에 있어서, 상기 막이 광학적 비선형 물질을 포함하는 것을 특징으로 하는 유기 막.
  16. 기판상에 유기 박막을 형성하는 장치에 있어서,
    반응 챔버;
    상기 반응 챔버를 거의 감싸는 가열기;
    상기 반응 챔버내로 연장된 배관; 및
    상기 반응 챔버에 부착된 진공 펌프
    를 포함하는 것을 특징으로 하는 장치.
  17. 제 16 항에 있어서, 상기 반응 챔버가 반응기 튜브를 포함하는 것을 특징으로 하는 장치.
  18. 제 16 항에 있어서, 상기 가열기가 멀티-존 가열기/냉각기인 것을 특징으로 하는 장치.
  19. 제 16 항에 있어서, 상기 배관이;
    제 1 단부와 제 2 단부를 구비하고 상기 제 2 단부가 상기 반응 챔버내부로 연장된 튜브; 및
    상기 튜브의 제 1 단부에 연결된 가스 원(gas source)
    을 포함하는 것을 특징으로 하는 장치.
  20. 제 19 항에 있어서, 상기 튜브의 내부에 위치된 개방 컨테이너를 더 포함하며, 상기 개방 컨테이너가 유기 프로커서 물질을 보유하는 것을 특징으로 하는 장치.
  21. 제 20 항에 있어서, 상기 튜브가 압력 조절기와 밸브를 포함하는 것을 특징으로 하는 장치.
  22. 제 16 항에 있어서, 상기 배관이;
    제 1 단부와 제 2 단부를 구비하고, 상기 제 2 단부가 상기 반응 챔버 내부로 연장된 제 1 튜브;
    상기 제 1 튜브의 제 1 단부에 연결되어, 유기 프로커서 물질을 수납하기 위한 거품발생기;
    제 1 단부와 제 2 단부를 구비하고, 상기 제 2 단부가 상기 거품발생기에 연결된 제 2 튜브; 및
    상기 제 2 튜브의 제 1 단부에 연결된 가스 원
    을 포함하는 것을 특징으로 하는 장치.
  23. 제 22 항에 있어서, 상기 제 2 튜브가 압력 조절기와 밸브를 포함하는 것을 특징으로 하는 장치.
  24. 제 16 항 에 있어서, 상기 기판에 접촉되는 온도 조절 블록을 포함하며, 상기 온도 조절 블록이 상기 온도 조절 블록내에 채널을 구비하는 것을 특징으로 하는 장치.
  25. 제 16 항에 있어서, 상기 반응 챔버에 부착된 트랩을 더 포함하는 것을 특징으로 하는 장치.
  26. 제 16 항에 있어서, 상기 반응기내에 제 1 롤 및 제 2 롤을 더 포함하며, 상기 기판을 상기 제 1 과 제 2 롤들 사이로 통과시키는 것을 특징으로 하는 장치.
  27. 기판상에 유기 박막을 형성하는 장치에 있어서,
    반응 챔버;
    상기 반응 챔버 내부로 연장된 크누센 셀;
    상기 기판에 연결되며 회전될 수 있는 샘플 홀더; 및
    상기 반응 챔버에 부착된 진공 펌프
    를 포함하는 것을 특징으로 하는 장치.
  28. 제 27 항에 있어서, 상기 반응 챔버 내부로 연장되는 배관을 더 포함하며, 상기 배관이,
    제 1 단부와 제 2 단부를 구비하고 상기 제 2 단부가 상기 반응 챔버 내부로 연장된 제 1 튜브;
    상기 제 1 튜브의 상기 제 1 단부에 연결되며 유기 프로커서 물질을 수납하기 위한 거품발생기;
    제 1 단부와 제 2 단부를 구비하고 상기 제 2 단부가 상기 거품발생기에 연결된 제 2 튜브; 및
    상기 제 2 튜브의 제 1 단부에 연결된 가스 원;
    을 포함하는 것을 특징으로 하는 장치.
  29. 제 27 항에 있어서, 상기 제 1 튜브가 가열되는 것을 특징으로 하는 장치.
  30. 제 27 항에 있어서, 상기 반응 챔버에 냉각된 덮개를 더 포함하는 것을 특징으로 하는 장치.
  31. 제 27 항에 있어서, 상기 박막의 두께를 측정하는 센서를 더 포함하는 것을 특징으로 하는 장치.
  32. 제 31 항에 있어서, 상기 센서가 석영 결정체인 것을 특징으로 하는 장치.
  33. 제 27 항에 있어서, 상기 반응 챔버에 연결된 로드-로크를 더 포함하는 것을 특징으로 장치.
  34. 제 27 항에 있어서, 상기 진공 펌프가 터보분자 펌프인 것을 특징으로 하는 장치.
  35. 제 27 항에 있어서, 상기 반응 챔버에 제 1 롤 과 제 2 롤을 더 포함하며, 상기 제 1 및 제 2 롤들 사이로 상기 기판이 통과되는 것을 특징으로 하는 장치.
  36. 기판상에 유기 박막을 형성하는 장치에 있어서,
    로딩 챔버와 유기 층 증착 챔버를 포함하는 다수의 진공 챔버들; 및
    상기 다수의 진공 챔버를 통과하고 기판을 구비한 컨베이어 벨트
    를 포함하는 것을 특징으로 하는 장치.
  37. 제 36 항에 있어서, 상기 유기 층 증착 챔버가 반응 가스 분배기를 포함하는 것을 특징으로 하는 장치.
  38. 제 36 항에 있어서, 상기 유기 층 증착 챔버가 가열기를 포함하는 것을 특징으로 하는 장치.
  39. 제 36 항에 있어서, 접촉 증착 챔버를 더 포함하는 것을 특징으로 하는 장치.
  40. 기판상에 유기 박막을 형성하는 장치에 있어서,
    반응 챔버;
    상기 반응 챔버를 가열하는 수단들;
    상기 반응 챔버 내부로 유기 프로커서 물질들의 증기들을 유도하는 수단들; 및
    상기 반응 챔버에 압력을 대기압 보다 낮은 압력으로 감소시키는 수단들
    을 포함하는 것을 특징으로 하는 장치.
  41. OLED를 형성하는 방법에 있어서,
    증기 상인 다수의 유기 프리커서를 제공하는 단계; 및
    상기 다수의 유기 프로커서들을 대기보다 낮은 압력에서 반응시키는 단계를
    포함하는 것을 특징으로 하는 방법.
  42. 제 41 항에 있어서, 상기 유기 프로커서들이 발광 물질들인 것을 특징으로 하는 방법.
  43. 제 41 항에 있어서, 상기 반응 단계가 발광 물질을 형성시키는 것을 특징으로 하는 방법.
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