KR100189398B1 - 전계발광 소자 - Google Patents

전계발광 소자 Download PDF

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KR100189398B1
KR100189398B1 KR1019900702649A KR900702649A KR100189398B1 KR 100189398 B1 KR100189398 B1 KR 100189398B1 KR 1019900702649 A KR1019900702649 A KR 1019900702649A KR 900702649 A KR900702649 A KR 900702649A KR 100189398 B1 KR100189398 B1 KR 100189398B1
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electroluminescent device
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헨리 프렌드 리차드
헨리 부로그헤스 제레미
도나트 코너 브리들리 도날
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캠브리지 디스플레이 테크놀로지 리미티드
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof

Abstract

전계발광 소자는 적어도 하나의 공액 중합체로 된 얇고 조밀한 중합체 필름 형태의 반도체층(4), 반도체층의 제1 표면과 접촉하는 제1 접촉층(5), 반도체층의 제2 표면과 접촉하는 제2 접촉층(3)을 포함한다. 반도체층의 중합체 필름(4)은, 제1 접촉층에 대해 제2 접촉층을 양(+)으로 되게 하도록 반도체 층에 걸친 제1 및 2 접촉층 사이에 전기장을 인가함과 동시에, 전하 캐리어가 반도체층에 주입되고, 방사가 반도체층으로 부터 방출되는 외인성 전하 캐리어의 저집중도를 갖는다.
중합체 필름은 구조식(I)의 폴리(p-페닐렌비닐렌)[PPV]이고, 여기서 페닐렌 고리는 알킬(바람직하게는 메틸), 알콕시(바람직하게는 메톡시 또는 에톡시), 할로겐(바람직하게는 클로로 또는 브롬) 또는 니트로로 부터 개별적으로 선택된 각각의 하나 이상의 치환기를 선택적으로 갖는다.

Description

전계발광 소자
제1도는 공액(conjugated) 중합체를 얻기 위한 반응식을 나타낸 구조식 도면.
제2도와 제3도는 본 발명에 따른 전계발광 소자(electroluminescent device)의 개략도.
제4도는 제2도와 제3도에 의거하여 설명된 소자의 전계발광출력 그래프.
제5도와 제6도는 본 발명의 다른 실시예에 따른 전계발광 소자에 대해 제각기 전류흐름 대 광방출, 출력강도 대 인가전압의 그래프.
제7도와 제8도는 제각기 본 발명의 또다른 실시예의 전류출력과 전계발광강도를 나타낸 그래프.
* 도면의 주요부분에 대한 부호의 설명
1 : 기판 2 : 제1전하 주입 접촉층
3 : 산화층 4 : 중합체 필름
5 : 제2전하 주입 접촉층
본 발명은 전계발광(EL) 소자에 관한 것으로, 특히 발광층이 반도체인 전계발광 소자에 관한 것이다.
전계발광(EL) 소자들은 전기장이 인가될시에 발광하는 구조물이다. 이와 같이 사용된 반도체에서 물리적인 처리를 위한 일반적인 모델은 대향 전극으로부터 반도체에 주입되는 전자-정공쌍의 방사결합을 이용한다. 일반적인 예로서, GaP에 의한 발광 다이오드와 III-V로 구성된 반도체가 있다. 비록 전계발광(EL) 소자들이 효과적이고 널리 사용될지라도, 그것들은 크기면에서 제한되고 대규모 표시소자에 경제적인 측면에서 쉽게 사용되지 않는다. 광범위한 영역에 제공될 수 있는 대체성 물질이 알려졌고, 무기 반도체중에서 대부분이 ZnS에 집중되어 왔다. 이 시스템은 고려해야 할 실제의 결점, 즉, 근본적으로 신뢰도가 낮다. ZnS의 메카니즘은 강전계하에서 반도체를 통하는 한 형태의 캐리어의 가속이 방사방출을 통하여 완화되는 반도체의 국부 여기를 야기시키는 경우라 생각된다.
유기물질중에서, 안트라센, 페릴렌, 코로넨과 같은 간단한 방향족 분자는 전계발광을 나타내는 것으로 알려져있다. ZnS와 같은 물질이 갖는 어려움은 유기층 및 전류-주입 전극층의 증착에 어려움과 함께 신뢰도가 낮다는 것이다. 유기물질의 승화(sublimation)와 같은 기술은 합성(resultant)층이 연성이고, 재결정화 되기 쉽고, 상부 접촉층의 고온 증착을 지지하기가 어려운 단점을 지닌다. 적당하게 변경된 방향족의 랭뮤어-블로지트 필름 증착과 같은 기술은 저질필름, 활성 물질의 희석(dilution), 제조비용의 고가를 초래한다.
안트라센을 이용하는 전계발광 소자는 미국특허원 제3,621,321호에 기술되어 있다. 이 소자는 고전력소모와 낮은 발광을 초래한다. 개선된 소자를 제공하기 위한 시도에 있어서, 미국특허원 제4,672,265호에는 발광층과 같은 이중층 구조를 지닌 EL 소자가 기술되어 있다. 그러나, 이중층 구조를 위해 제안된 물질은 위에서 언급한 단점을 초래하는 유기물이다.
본 발명은 위에서 언급한 단점이 제거되거나 최소한 완화되는 전계발광 소자를 제공하는 것이다.
본 발명은 적어도 하나의 공액(conjugated) 중합체로 된 얇고 조밀한 필름 형태의 반도체층, 반도체층의 제1표면과 접촉하는 제1접촉층 및 반도체층의 제2표면과 접촉하는 제2접촉층으로 구성된 전계발광 소자를 제공하는데, 상기 반도체층의 중합체 필름은, 제1접촉층에 대해 제2접촉층을 양(+)으로 되게하도록 반도체층에 걸친 제1 및 2접촉층사이에 전기장을 인가함과 동시에, 전하 캐리어가 반도체층에 주입되고, 방사가 반도체층으로부터 방출되는 외인성(extrinsic) 전하캐리어의 저집중도(concentration)를 갖는다.
본 발명은 반도체 공액 중합체가 적당한 접촉층으로부터 전하 캐리어의 주입으로 전계발광을 유발시킬 수 있도록 야기시킬 수 있는 발견에 기초로 한다.
반도체 공액 중합체는 그 자체로 알려져 있다. 예를 들면, 광변조기에서의 사용법은 유럽특허원 제0294061호에 기술되어 있다. 이런 경우에, 폴리아세틸렌은 제1전극과 제2전극사이의 변조구조에서 활성층으로 사용된다. 광변조 효과를 일으키는 활성층에 공간 전하 영역을 만들기 위하여 하나의 전극과 활성층 사이에 절연층을 배치하는 것이 필요하다. 이와 같은 구조는 전계발광을 표시하지 않는다. 왜냐면 공간 저하층의 존재가 방사성 붕괴가 일어나는 전자-정공 쌍의 형성을 방해하기 때문이다. 유럽특허원 제0294061호에서 전계발광 표시가 전체적으로 바람직하지 않는 것은 분명하다. 왜냐하면 광변조 효과가 그것에 의해서 분열되기 때문이다.
본 발명의 소자에서, 공액 중합체는 양호하게도 폴리(p-페닐렌비닐렌)[PPV]가 바람직하고, 제1전하 주입 접촉층은 한면이 얇은 산화층으로된 얇은 알루미늄 층이고, 반도체층의 제1표면은 상기 산화층과 접촉하며, 제2전하 주입 접촉층은 알루미늄 또는 금으로 된 얇은 층이다.
다른 실시예에서, 공액 중합체는 PPV이고, 제1접촉층은 알루미늄 또는 마그네슘 및 은의 합금이고, 제2접촉층은 산화인듐이다.
또다른 실시예에서, 공액 중합체는 PPV이고, 하나의 접촉층은 비결정 실리콘이고, 다른 하나의 접촉층은 알루미늄, 금, 마그네슘 / 은 합금과 산화인듐으로 구성된 군에서 선택된다.
이런 실시예는 제1접촉층 또는 제2접촉층의 어느 하나를 기판상에 놓고, PPV의 박막을 인가하여, 제1 및 2 접촉층의 다른 하나를 놓음으로써 행해질 수 있다.
양호하게도, 중합체 필름은 10내지 5범위의 균일한 두께를 지니고, 공액 중합체는 1eV 내지 3.5eV 범위의 반도체 대역갭을 갖는다. 더욱이 중합체 필름의 발광영역에서의 공액 중합체 비율은 필름에 제공된 공액 중합체에서 전하 이동을 위한 침투임계(percolation threshold)를 성취하기에 충분하다.
본 발명의 두번째 양상은 전계발광소자 제조방법을 제공하는데, 적어도 하나의 공액 중합체로 이루어진 조밀한 중합체 필름의 얇은 층의 형태의 반도체층은 기판상에 얇은 중합체 필름으로서 전구 중합체의 얇은층을 증착한 다음 공액 중합체를 형성하도록 고온으로 증착된 전구 중합체를 가열하는 단계로 기판상에 증착되고, 제1접촉층의 얇은층은 반도체층의 제1표면과 접촉하고, 제2접촉층의 얇은층은 반도체층의 제2 접촉층을 양(+)으로 되게 하도록 반도체층과 접촉한 제1 및 2접촉층사이에 전기장을 인가할 시에 전하 캐리어가 반도체층에 주입되고, 방사가 반도체층으로부터 방출되는 외인성전하캐리어의 저집중도를 갖는다.
공액 중합체는 중합체 골격(backbone)을 따라 비국부(delocalised) π-전자 시스템을 지닌 중합체를 의미하는데, 이런 비국부 π-전자 시스템은 중합체에 반도체 특성을 수여하고, 중합체 체인을 따라 높은 이동성을 지닌 양(+) 및 음(-)의 전하 캐리어를 지지하는 능력을 중합체에 제공한다. 그와 같은 중합체는 R.H.Friend에 의한 Journal of Molecular Electronics 4 (1988) January-March, No. 1, pages 37 to 46 에 예로 논의되어 있다.
본 발명에 따른 메카니즘은 양(+)의 접촉층이 중합체 필름에 양(+)의 전하 캐리어를 주입하고, 음(-)의 접촉층이 중합체 필름에 음(-)의 전하 캐리어를 주입하는 것으로 되어 있는데, 이 전하 캐리어는 방사적으로 자연붕괴되는 전하 캐리어 쌍을 형성하도록 결합한다. 이것을 성취하기 위하여, 양호하게도, 양(+)의 접촉층은 높은 일함수(work function)를 갖도록 선택되고, 음(-)의 접촉층은 낮은 일함수를 갖도록 선택된다. 중합체 반도체층과 접촉하고, 회로에 걸쳐 외부전위의 인가를 통해 중합체 반도체에 대하여 음(-)으로 될시에 음의 접촉층은 중합체 반도체층에 전자를 주입하는 전자-주입물질, 예를 들면 금속 또는 도핑된 반도체로 구성된다. 중합체 반도체층과 접촉되고, 회로에 걸쳐 외부전위의 인가를 통해 중합체 반도체에 대하여 양(+)으로 될시에 양(+)의 접촉층은 중합체 반도체층에 일반적으로 정공이라하는 양(+)의 전하를 주입하는 정공-주입물질, 예를들면 금속 또는 도핑된 반도체로 구성된다.
바람직한 전계발광을 일으키게 하기 위하여, 중합체 필름은 무방사 재결합중심(centre)으로 작용하는 결함이 실질적으로 없어야 한다. 왜냐하면 그와 같은 결함은 전계발광을 방해하기 때문이다.
조밀한 중합체 필름은 중합체 필름이 미소섬유(fibrillar)가 아니고 실질적으로 기공이 없음을 의미한다.
하나 또는 각각의 접촉층은 전하 주입 물질층에 추가하여, 다른 물질층, 양호하게는 EL 층에 전자 및 정공의 주입비를 제어하고, 방사성 자연붕괴가 접촉층의 전하 주입 물질과 떨어져 확실히 일어나는 유기물질을 포함한다.
공액 중합체의 필름은 양호하게도 공액 중합체의 단편을 포함하는 단독 공액 중합체 또는 단독 공중합체로 구성된다. 선택적으로, 고액 중합체의 필름은 다른 적당한 중합체를 갖는 공액 중합체 또는 공중합체의 혼합물로 구성된다.
더 양호한 중합체 필름의 특징은 다음과 같다.
(i) 중합체는 산소, 습기가 안정하고, 고온으로 노출된다.
(ii) 중합체 필름은 하부층에 대한 양호한 점착성, 열유도 및 응력 유도 크래킹(cracking)에 대한 양호한 저항성과, 수축, 팽창, 재결정 또는 다른 형태 변화에 대한 양호한 저항성을 갖는다.
(iii) 중합체 필름은 예를 들면 고온 결정 및 고온 용융에 의해 이온/원자 이동과정에 탄력 있다.
본 발명의 실시예는 첨부된 도면에 의거하여 설명할 것이다.
공액 중합체의 필름은 다음 구조식의 폴리(p-페닐렌비닐렌)[PPV] 필름이 바람직하다.
상기식에서 페닐렌 고리(ring)는 알킬(바람직하게는 메틸), 알콕시(바람직하게는 메톡시 또는 에톡시), 할로겐(바람직하게는 클로린 또는 브로민), 또는 니트로로부터 각각 선택된 하나 이상의 치환기를 선택적으로 갖는다.
폴리(p-페닐렌비닐렌)로부터 유도된 다른 공액 중합체는 또한 본 발명의 EL 소자에서 중합체 필름으로서 사용하는 데에 적합하다. 이와 같이 유도물의 예는 (i) (ii) (iii)에 의해 유도된 중합체이다 :
(i) 식 (I)에서의 페닐렌 고리를 융합고리계로 대치, 예를 들면 다음과 같은 구조식을 제공하는 안트라센 또는 나프탈렌 고리계로 페닐렌 고리를 대치한다.
이것들의 대체가 되는 고리계는 또한 페닐렌 고리에 관하여 위에서 설명한 형태의 하나 이상의 치환기를 갖는다.
(ii) 아래와 같은 구조식을 제공하는 푸란 고리와 같은 이종환식(heterocyclic)고리계로 페닐렌 고리를 대치한다.
앞에서와 같이, 푸란 고리는 페닐렌 고리에 관하여 위에서 설명한 형태의 하나 이상의 치환기를 갖는다.
(iii) 아래와 같은 구조식을 제공하는 각각의 페닐렌 고리 (또는 (i)과 (ii)에서 위에 설명한 각각의 다른 대체 고리계)와 관련된 비닐렌일부분의 수가 증가한다.
상기식에서 y는 2, 3, 4, 5, 6, 7, ……을 나타낸다.
다시 한번, 고리계는 위에서 언급한 다양한 치환기를 갖는다.
이것들의 여러가지 다른 PPV 유도물은 다른 반도체 에너지 갭을 가지면, 이는 스펙트럼의 전체가시부분을 커버(cover)하는 다른 파장에서 방출하는 전계발광 소자를 구성하게 한다.
공액 중합체의 필름은 용액 처리할 수 있거나 용융 처리할 수 있는 전구물질 중합체의 화학 및 / 또는 열처리에 의해 준비될 수 있다. 후자는 방출반응을 거쳐 공액 중합체로 변형되기 전에 바람직한 형태로 정제되거나 미리 처리될 수 있다.
위에서 설명한 PPV의 다양한 유도물의 필름은 적당한 술포늄(sulphonium)전구물질을 사용하므로써 유사한 방법으로 전도성 기판상에 적용될 수 있다.
어떤 상황에서, 술포늄 염 전구물질 (III)보다 유기용매에서 더 높은 용해도를 갖는 중합체 전구물질을 사용하는 것이 유리할 것이다. 유기용매의 향상된 용해도는 알콕시군(일반적으로 메톡시), 또는 피리디늄군과 같은 더 적은 친수성(hydrophilic)군으로 전구물질의 술포늄 일부분을 대치하므로써 성취될 수 있다.
통상적으로, 폴리(페닐린비닐렌)의 필름은 제1도에 도시한 바와 같이 반응도표에 의존하는 방법으로 전도성 기판상에 붙여진다. 술포늄 염 모노머(II)는 수성 용액 또는 메탄올/물의 용액의 전구 중합체(III)나 메탄올로 전환된다. 이와 같은 전구 중합체(III)의 용액은 포토레지스트 처리를 위한 반도체 산업에서 사용된 바와 같이 표준 스핀식-코팅 기술에 의해 전도성 기판상에서 인가될 수 있다. 전구 중합체(III)의 합성필름은 200내지 350℃ 범위의 온도로 가열하므로써 폴리(페닐렌비닐렌)(I)으로 전환될 수 있다.
모노머(II)의 화학합성에 필요한 조건의 세부사항, 전구물질(III)에 대한 중합과 PPV에 대한 열전환은 조사 보고서, 예를 들면 [D.D.C. Bradley J. Phys. D (Applied Physics), 20, 1389 (1987) ; and J.D. Stenger Smith, R.W. Lenz and G. Wegner, Polymer 30, 1048 (1989)]에 기술되어 있다.
10내지 10두께의 폴리(페닐렌비닐렌) 필름이 얻어질 수 있음을 발견하였다. 이 PPV 필름들은 작은구멍이 거의 없음을 알았다. PPV 필름은 약 2.5eV (500)의 반도체 에너지 갭을 갖고 ; PPV 필름은 튼튼하고, 실온에서 산소와 거의 반응하지 않으며, 300℃ 초과한 온도에서 공기없이도 안정하다.
공액 물질의 향상된 정리정돈(ordering)은 추가 중간구조의 생성없이 단순 반응을 거쳐 순조롭게 방출진행을 보장하도록 전구중합체의 이탈(leaving)군을 변경시키므로써 성취될 것이다. 따라서, 예를 들면, 정상 디알킬 술포늄 부분은 테트라히드로티오페늄 부분으로 대치할 수 있다. 테트라히드로티오페늄 부분은 알킬 머캅탄에 디알킬 술파이드로 알 수 있는 바와 같이, 알킬머캡탄(mercaptan)으로 분해없이 단일 이탈군으로 방출한다. 여기 기술한 예에서, 사용된 전구중합체는 이탈군으로서 디메틸 술파이드와 테트라히드로 티오펜 양자를 포함한다. 전구물질양자 모두는 아래 예에서 도시된 소자 구조에서 사용에 적당한 PPV필름을 생성시킨다.
공액 중합체의 필름을 형성하기에 적당할 다른 물질은 폴리(페닐렌)이다.
이 물질은 5,6-디히드록시클로헥사-1,3-디엔의 생물학적 합성 유도물로부터 개시하므로써 조제될 수 있을 것이다. 이 유도물은 단순 유기용매에 녹기쉬운 중합체 전구물질로 라디칼 개시인자(radical initator)의 사용으로 중합될 수 있다. 이 폴리(페닐렌)의 조제는 [Ballard et al, J. Chem. Soc. Chem. 954 (1983)]에 충분히 기술되어 있다.
중합체 전구물질의 용액은 전도성 기판상에 박막으로 스핀식-코팅되어, 통상적으로 140 내지 240℃의 열처리로 공액 폴리(페닐렌)중합체로 변형된다.
비닐 또는 디엔 모노머로된 공중합은 또한 페닐렌 공중합체를 얻기 위해 실행될 수 있다.
공액 중합체의 필요한 필름을 형성하기 위해 사용될 수 있는 다른 종류의 물질은 주공액체인에 부착된 벌키펜던트사이드군(bulky pendent side groups)의 존재에 의해 또는 하나 이상의 성분이 공액을 이루지 않는 공중합체 구조내에 공액 중합체의 함유물에 의해 용액 처리가능하거나 용융 처리 가능한 것 중 어느 하나인 공액 중합체이다. 용액처리가능한 실시예는 다음을 포함한다 :
(a) 폴리(4,4'-디페닐렌디페닐비닐렌)[PDPV]는 둘의 비닐렌 카본이 페닐고리로 치환되는 아릴렌 비닐렌 중합체이다. 그것은 일반 유기용매에 용해될 수 있다. 따라서 박막의 제조를 가능케 한다.
(b) 폴리(1,4-페닐렌-1-페닐비닐렌)와 폴리 (1,4-페닐렌디페닐 비닐렌)중합체들은 PPV의 유사체이고, PPV에서 하나와 둘의 비닐렌카본 각각은 페닐군으로 치환된다. 그것들은 유기용매에서 둘 다 용해될 수 있고, 박막형태로 주조되거나 만들어진다.
(c) 폴리(3-알킬티오펜) 중합체 (알킬은 프로필, 부틸, 펜틸, 헥실, 헵틸, 옥틸, 데실, 운데실, 도데실중에서 하나이다)는 일반 유기용매에서 용액처리가능하고, 긴 알킬 시퀸스(옥틸과 같거나 옥틸보다 큰 알킬)에 대하여는 또한 용융처리 가능하다.
(d) 폴리(3-알킬피롤) 중합체는 폴리(3-알킬티오펜) 중합체와 유사하도록 되어 있다.
(e) 부틸보다 큰 알킬을 갖는 폴리(2,5-디알콕시-p-페닐렌비닐렌) 중합체는 용액처리 가능하다.
(f) 폴리(페닐아세틸렌)는 체인을 따르는 히드로겐 원자가 페닐군으로 대치되는 폴리아세틸렌의 유도물이다. 이 치환은 물질을 용해할 수 있게 한다.
어떤 상황에서, 중합체의 필요한 처리가능성을 얻어, 전도성 기판 (전하 주입 접촉층)상에 중합체의 필요한 규닐박막의 형성을 용이하게 하도록 다른 중합체와 공액 중합체의 중합체 혼합물을 형성하는데 적당할 수 있다.
그런 공중합체 또는 중합체 혼합물이 공액 중합체의 필름을 형성하는데 사용될 때, 공액 중합체의 상기 필름을 합체하는 전계발광 소자의 활성영역은 공중합체 또는 중합체 혼합물의 침투임계(percolation threshold) 같거나 보다 큰 공액 중합체의 체적부분을 포함한다.
반도체 전계발광층은 서로 다른 대역 갭 및/또는 대다수 전하종류를 갖는 중합체의 층으로 복합층으로서 형성됨으로써, 예를들어, EL 소자의 특정영역내에서 전하 주입 접촉층으로부터의 주입 전하의 집중도가 성취될 수 있다. 복합층은 중합체 층의 연속적인 증착으로 제조될 것이다. 필름이 스핀식 또는 드로우-코팅(draw-coating)에 의해 전구물질의 형태로 공액 중합체에 증착되는 경우에, 공액 중합체에 대한 전환공정은 필름을 용해되지 않게 함으로써 연속적인 층은 앞서 증착된 필름을 용해없이 유사하게 적용될 것이다.
지금부터 제2도와 제3도를 참조로, EL 소자는 아래와 같이 구성된다 : 대략 1두께의 유리, 예를 들면 실리카 또는 규산화붕소 유리(1)의 기판 상부표면상에 제1전하 주입 접촉층(2)이 형성된다. 전하 주입 접촉층은 섀도 마스크를 통해 알루미늄을 열진공증착(evaporation)시켜 형성되고, 그 결과 대략 20두께의 층으로 형성된다. 섀도 마스크는 2폭, 2간격과 15길이의 일련의 병렬 스트립의 패턴을 한정하는데에 사용되었다. 그 결과 알루미늄으로 된 전하 주입 접촉층은 얇은 표면의 산화층(3)의 형성을 허용하도록 노출된다. 그 다음 전자 주입 접촉층이 형성된다.
10 내지 25㎖ 메탄올에서 1 그램중합체 농도를 갖는 PPV 에 대한 전구물질의 용액은 위에서 기술한 조합 기판상에 스핀식 코팅된다. 스핀식 코팅은 조합 기판의 전체표면위로 중합체 용액을 퍼지게 한 다음 5000r.p.m의 속도에서 수직축에 대해 상부표면이 수평으로 유지된 기판을 스핀함으로써 성취된다. 복합기판과 전구중합체층은 300℃에서 12시간 동안 진공오븐에서 가열된다. 이 열처리는 전구중합체를 PPV로 로 전환시키고, 복합 PPV 필름(4)는 100 내지 300두께를 갖는다. 필름두께에 대한 최소한의 요구조건은 필름 전도성으로 설정되고, 최저 한계는 20이다. 그러나, 바람직한 두께는 20내지 1이다.
제2전하 주입 접촉층(5)은 PPV 필름상에 금 또는 알루미늄을 진공 증착시키므로 형성된다. 섀도 마스크는 다시 PPV 필름의 표면상에 패턴을 한정하는데에 사용되므로, 2폭, 2간격과 2길이의 일련의 병렬스트립이 제1전하 주입 접촉층 스트립에 직각으로 회전되어 형성된다. 제2전하 주입 접촉층의 두께는 20 내지 20이다. 이렇게 형성된 것은 정공 주입 접촉층이다.
소자의 평면에 직각인 EL 소자로부터의 발광을 허용하기 위해 적어도 하나의 전하 주입 접촉측은 투명하거나 반투명한 것이 바람직하다. 이것은 30를 초과하지 않는 두께의 알루미늄 및 금으로된 층으로 성취된다. 약 200의 PPV층의 두께를 가진 소자에 대하여, 강전계발광과 전하 주입을 위한 임계 전압은 약 40 볼트이다.
이 전압은 2×106V -1임계 전계를 제공한다. 2㎃/㎠ 전류 및 도에서 반투명 전극을 통하는 발광은 정상 광조건하에서 눈으로 볼 수 있다. 소작의 출력은 100㎑의 주파수에 의한 의존성이 약하다는 것을 나타낸다. 이것은 EL 소자의 응답시간이 매우 짧거나 10㎲보다 빠르다는 것을 설명한다. 사용시 EL 는 성능저하를 예방하는 특정조처 없이 공기로 동작된다.
소자의 광출력은 회절 격자 모노크로마터(grating monochromator)에 의해 스펙트럼으로 분해되고, 실리콘 광기전 셀로 검출되며, 그 측정은 실온(20℃)에서와 또한 저온에서 광도달로 크라이오스탯(cryostat)에 보유되는 소자에 의해 실행된다. 그 결과는 제4도에 도시한 바와 같다. EL 스펙트럼은 약 0.15eV로 분리되고, 온도를 위치가 약간 시프트하는 피크를 갖는 690 내지 500(1.8 내지 2.4eV) 스펙트럼의 범위에 걸친 광출력을 나타낸다.
EL 층에 관해 낮은 일함수를 갖기 때문에 전자-주입 접촉층으로 사용하기에 알맞은 다른 물질은 n-도핑 실리콘(비결정 또는 결정체), 산화 코팅으로 된 실리콘, 순수금속이거나 Ag 와 같은 다른 액 중합체의 얇은층은 전자-주입 접촉층을 형성하도록 금속층과 전계발광 중합체층 사이에 삽입될 수 있다.
EL 층에 대해 높은 일함수를 갖기 때문에 정공-주입 접촉층으로 사용하기에 알맞은 다른 물질은 (스펙트럼의 가시부에서 투명한) 인듐/주석 산화물 백금, 니켈, 팔라듐과 흑연이다. 또한 전기화학적으로 중합된 폴리피롤 또는 폴리티오펜 등이 p형 도핑 공액 중합체의 얇은층은 정공-주입 접촉층을 형성하도록 금속층과 전계 발광 중합체층 사이에 삽입될 수 있다.
위에서 언급한 물질들은 다음과 같이 적용될 것이다 : 백금과 같이 아주 높은 용융점 온도를 가진 금속을 제외한 모든 금속은 진공 증착법에 의해 증착될 것이고 ; 인듐/주석 산화물을 포함하는 모든 금속은 DC 또는 RF 스퍼터링법과 또한 전자 빔 진공 증착법을 이용하여 증착되며 ; 비결정 실리콘 증착은 포스핀등의 실란과 도펀트의 혼합물로부터 글로 방전 증착으로 행해질 것이다.
다음은 이 물질의 사용하는 구조의 다른 실시예이다.
[실시예 2]
이 실시예의 구조는 유리기판상의 일련의 층으로 구성된다. 첫째, 투명한 산화인듐을 전도하는 층은 산소가 존재하는 인듐 표적으로부터 이온-빔 스퍼터링 법을 포함하는 공정에 의해 기판상에 증착된다.
실시예들은 10-8mbar의 베이스 압력을 갖는 저온펌프계에서 입안된다. 기판은 수냉식이고, 여기서 사용된 모든 증착동안 실온에 존속한다. 통상적으로 2×10-4mbar의 산소압력이 있을시에, 통상적으로 0.1/sec 의 증착율에서 인듐 과녁으로부터의 이온-빔 스퍼터링은 통상적으로 5×10-4Ω의 고유저항을 갖는 투명한 산화 인듐의 필름을 생성한다. 통상적으로 100의 두께는 약 50Ω/㎡ 의 시트 저항을 제공한다. 이와 같은 필름은 90%이상의 스펙트럼의 가시부분에서의 광전송계수를 갖는다.
이 필름들은 X선과 전자회절측정으로부터 결정된 비결정 구조를 갖는다.
PPV의 층은 실시예 1에서 전술된 과정을 이용하여 산화인듐층상에 증착된다. 알루미늄으로 된 상부 접촉층은 50두께로 진공 증착법에 의해 마지막으로 증착된다. 이 구조는 양(+)의 접촉층 역할을 하는 산화인듐 접촉층과, 음(-)의 접촉층 역할을 하는 알루미늄 접촉층으로 동작한다. 발광은 산화인듐층을 통해 조사된다.
이런식, 70두께를 갖는 PPV의 층과, 2㎟의 활성영역으로 구성된 구조의 결과는 제5도와 제6도에 도시되었다. 발광과 관련된 전류흐름의 임계는 제5도에서 약 14V로 보여진다. 소자에 대한 스펙트럼통합광출력의 강도의 변화는 제6도에서 전류의 함수로 도시된다.
[실시예 3]
이 구조의 제조는 최상부 금속 접촉층에 이르기까지 상기 실시예 2에 관한다. 여기서, 음(-)의 접촉층 역할을 하는 상부 접촉층을 형성하도록 은과 마그네슘의 합금을 진공 증착법으로 증착시킨다. 진공증착법은 보우트(boat)에서 1 대 10의 몰비(molar ration)로 은과 마그네슘 분말의 혼합물을 가열하므로써 실행되고, 통상적으로 50두께의 필름이 증착된다.
마그네슘은 낮은 일함수를 갖는 음(-)의 전극에 대한 물질로 바람직하다. 합금을 형성하는 은의 가산으로 중합체층에 대한 금속 필름의 부착성이 향상되고, 산화에 대한 저항성이 향상된다. 이런 샘플의 전류/전압 및 EL 성질은 실시예 2 에서 기술한 것들과 유사하다.
[실시예 4]
이들 구조는 음(-)의 전극으로 작용하는 비결정 실리콘-히드로겐 합금과 양(+)의 전극으로 작용하는 산화인듐으로 된 층으로 제조되었다. 유리기판은 알루미늄 또는 크롬의 증착된 금속 접촉층으로 사용된다. 비결정 실리콘-히드로겐 필름은 아래에 상세히 기술되는 바와 같이 무선주파수(RF)스퍼터링에 의해 증착된다.
RF 스퍼터기는 두개의 타겟을 갖는데, 그 타겟은 액체질소로 냉각된 게터(getter)가 사용되고 8간격의 타겟-기판으로서 동작한다. 챔버는 5×10-8mbar의 베이스압력을 갖는다. 마그네트론 타겟은 3두께의 n도핑 Si 웨이퍼의 층으로 채워진다. 타켓은 샘플 증착에 앞서 1 내지 2시간 동안 미리 스퍼터링하므로써 세척된다. 위에서와 같이 준비된 기판은 방사적으로 가열되므로 3두께의 Cu 와 Al 기판의 뒷쪽 온도는 250 내지 300℃이다. 기판은 약 6회 역전환/분 회전한다. 스퍼터링 가스는 0.007 내지 0.013mbar 압력의 아르곤에서 30% H2가 사용되고 증착되는 동안 챔버를 통해 계속해서 지나간다. RF 전력은 2W 반사력으로 250W를 사용한다. 증착율은 통상적으로 1시간 30분의 증착시간동안 1필름 두께를 제공하는 12/분이다.
결과적으로 비결정 Si는 불그스레한 브라운 색상이고, 5×106과 5×108Ω사이의 d.c. 저항률을 갖는다. [이것은 샘플위 또는 아래의 하나이고, 3길이와, 0.25간격을 갖는 두개의 Al 패드를 진공 증착시키고, 이런 두개의 접촉층사이의 저항을 측정하므로써 발견하였다] : PPV 층은 위의 실시예 1에서 기술한 바와 같이 비결정 실리콘-히드로겐 층에 인가되고, 이것은 실시예 2에서 기술한 절차를 이용하여 PPV 층상에 직접적으로 증착된 산화인듐층을 인가하는 동작에 선행한다.
위에서 나타낸 단계를 사용하여 제조된 구조를 얻기 위한 결과는 실리콘-히드로겐 1, PPV 40, 산화인듐 250두께를 갖는 층과 14㎡ 영역을 갖는 구조를 제7도와 제8도에 도시하였다. 제7도는 순방향 바이어스 (양(+)의 산화인듐)의 소자에 대한 전류 대 전압특성을 도시하였고, 제8도는 전류와 집적된 광출력의 변동을 도시하였다. 전하 주입과 발광의 시작은 약 17V 에서이고, 이런 임계치이상의 전류의 상승은 저항성 실리콘-히드로겐 층이 여기에 존재하기 때문에 제5도에서 실시예로 보인 바와 같이 실리콘-히드로겐 층없는 구조로 관찰되는 것보다도 점진적으로 일어난다.
겐 접촉에 의한 음(-)의 산화인듐 접촉)에서 EL이 더 약하게 보여진다. 그러나, 동작의 바람직한 모드는 순방향 바이어스이다.
[실시예 5]
실시예 4에서와 같은 제조방식이지만, 산화인듐의 상부 층은 반투명한 금 또는 알루미늄 층으로 대체된다.
약 20두께의 상부층으로 제조된 구조는 이런 상부 접촉을 통해 EL를 나타낸다. 이 소자는 위에서 논한 실시예와 유사한 특성을 보인다.
실시예 4의 제조방법은 실시예 2와 3에서 기술한 접촉층으로 또한 사용된다.
제조방법중 다른 제조방법은 실리콘-히드로겐 층과 산화인듐 층을 증착하기 위한 그 자체로 알려져있다. 실리콘에 대해 실란의 글로우 방전과 진공 증착을 포함하고, 산화인듐에 대해 다른 가능성은 여기서 사용된 산화인듐과 아주 유사한 전기적 성질을 갖는 ITO(indium tin oxide)를 형성하기 위해 주석과 인듐을 포함한다. 증착 방법은 진공증착법 RF 및 DC 스퍼터링법을 포함한다.
전하 주입 접촉층의 두께 선택은 사용되는 증착기술과 접촉층의 바람직한 광 투명도에 의해 결정될 것이다. 전하 주입의 용이함은 합성물로서 전하 주입 접촉층을 구성하므로써 향상될 것이다. 이와 같은 합성물은, 제각기 정공 및 전자 주입을 위한 산화 및 감소된 공액 중합체의 얇은층을 포함한다. 이런공액 중합체의 여분 층은 활성 전계발광 중합체 층과 같거나 같지 않을 수 있다. 이와 같은 물질의 도핑 방법은 본 기술분야에 공지되었고, T.J. Skotheim 에 의한 [Handbook of Conducting Polymers]에 명백히 기술되어 있다.
어떤 상황에서, 소자의 평면에 수직인 방사방출을 허용하기 위하여 적어도 하나의 전하 주입 접촉층이 투명하거나 반투명한 것이 바람직하더라도, 예를들어 소자의 평면내에서 방출이 요구되는 경우에 필요하지 않다.
제조된 EL 소자의 크기한계는 스핀식 코팅으로 사용될 수 있는 기판 크기로 결정된다. 예를 들면, 15직경의 실리콘 웨이퍼는 이런 방법으로 코팅되어 왔다. 아주 큰 영역을 코팅하기 위하여, 드로우-코팅과 같은 기술이 대신 사용될 것이다. 그러므로, 평방미터의 면적을 가진 공액 중합체를 이용한 EL 소자를 구성할 수 있다.
PPV를 포함하는 공액 중합체의 적어도 일부는 진공증착을 위해 고온으로 증착을 필요로 하는 금속층의 증착이나, 비결정 실리콘 층의 증착과 같은 포스트-프로세싱에 견딜 수 있음으로써, 활성 전계발광 영역의 한정을 위한 포토리소그라픽 공정에 견딜 수 있다.
PPV사용과 함께, 스핀 또는 드로우 코팅중의 어느 하나가 요구된 EL소자의 형태와 공액 중합체에 따라 기판에 전구 중합체를 인가하는 방법으로서 이용되는 것이 바람직할지라도, 스핀-코팅, 드로우-코팅과 용융-프로세싱은 기판상에 공액 중합체를 증착시키는 데에 사용될 모든 방법이다.
EL 소자는 전계발광이 유익한 여러가지 방식으로 사용될 것이다. 이는 반도체 LED가 통상적으로 사용되는 경우에 사용될 것이다. 전계발광 소자는 또한 통상적으로 액정이 사용되는 경우에 사용될 것이고, EL소자는 액정에 대해 바람직하게 선택되는 많은 성질을 갖고 있다.
EL 소자가 액정 표시소자와는 대조적으로 발광하므로, 시각이 넓다. 더욱이, 대규모 EL 소자는 기판의 평면 및 공간과 관련된 문제가 대규모 액정 표시 소자와 부닥쳤을 경우에 성취될 수 있다.
EL 소자는 특히 매트릭스-어드레스된 표시소자, 예를 들면 텔레비젼 및 컴퓨터 표시소자에 적당하다. 매트릭스-어드레스된 표시소자내에 사용하는 전계발광 소자의 일예는 제3도에 도시하였고, 여기에서, 전하 주입 접촉층은 반도체층의 어느 한측면에 스트립으로 인가되고, 한 접촉층의 스트립이 다른 접촉층의 스트립에 직교한다. 표시소자의 화소라 불리워지는 반도체 층의 영역 또는 개별 EL 소자의 매트릭스-어드레싱은 하부전하주입접촉층의 특정 스트립과 제1스트립에 직각인 상부 전하 주입 접촉층의 특정 스트립의 선택으로 성취된다. 더욱이, EL 소자가 높은 응답속도를 지니므로, EL 소자는 텔레비젼 스크린으로서 사용하는 데에 적당하고, 특히, 발광색상이 공액 중합체의 선택을 통해 제어될 것이므로, 반도체 대역 갭과, 녹색, 적색 및 청색 화소를 이용하여 색상 혼합에 적당한 칼라표시 소자는 EL 소자에서 서로다른 공액 중합체의 위치를 통해 가능하다.
EL 소자는 차량용 계기판, 예를들어 쿠커 또는 비디오 레코더상의 표시기에 대한 개별 형상소자로 사용될 수 있다. 각각의 소자는 의도한 응용에 대해 필요한 형상으로 제조될 수 있다. 더욱이, EL 소자는 편평할 필요가 없고, 제조후에, 3 차원에서의 외형 예를 들면 항공기 또는 차량에서 바람막이 유리의 외형에 따르도록 형성된다. 이와 같은 사용으로 인하여 전구 중합체는 폴리에스테르, 폴리비닐리덴 불화물 또는 폴리이미드 등의 투명한 중합체 필름과 같은 적당한 기판에 제공된다. 전구 중합체가 그런 유연한 중합체 필름에 제공될 경우, 롤(roll)상의 EL 소자의 연속적인 제조가 가능하다. 선택적으로 전구 중합체는 미리 제조되어 형성된 기판상에 드로우-코팅 공정을 이용하여 제공될 수 있다.
최종으로, EL 소자의 사용은 광통신에 생각할 수 있는데, 광통신에서 EL 소자는 광섬유 및/또는 박막 도파관과 EL 소자의 효과적인 광결합을 행하는 광원으로서 작용하도록 준비된 구조상에 직접적으로 제조될 수 있다. 유사한 출원은 [An article by Satoshi Ishihara in Science and Technology in Japan of July 1989, pages 8 to 14 entitled Optical Information Processing]에 기술되어 있다. EL 소자 광원은 레이저로 사용하는 것이 적당할 것이다.

Claims (26)

  1. 적어도 하나의 공액 중합체로 구성된 얇고 조밀한 중합체 필름 형태의 발광층.
    상기 발광층의 한측면상에 배치되어, 상기 소자에 전기장을 인가함과 동시에, 제1타입의 전하 캐리어가 발광층으로 주입되도록 선택된 제1접촉층과, 상기 발광층의 다른 측면상에 배치된 제2접촉층을 포함하는 전계발광소자에 있어서, 상기 제2접촉층은 상기 소자에 전기장을 인가함과 동시에, 제2타입의 전하 캐리어가 상기 발광층으로 주입되도록 선택되며, 상기 발광층은 중합체 필름의 전하 이동을 위한 침투임계가 성취되게 하는 체적부분에 제공된 반도체 공액 중합체를 포함하고, 상기 반도체 공액 중합체는, 제1접촉층에 대해 제2접촉층을 양(+)으로 되게하도록 발광층에 걸친 제1 및 제2접촉층사이에 전기장을 인가함과 동시에, 상기 제1 및 제2타입의 전하 캐리어가 발광층으로 주입되어지고, 상기 공액 중합체로부터 방사가 방출되도록 반도체공액 중합체내에 방사상 붕괴하는 전하 캐리어 쌍을 형성하도록 조합하는 외인성 전하캐리어의 저집중도를 가지는 것을 특징으로 하는 전계발광 소자.
  2. 제1항에 있어서, 상기 공액 중합체가 다음 구조식의 폴리(p-페닐렌비닐렌)[PPV]으로 구성되는데,
    상기 페닐렌 고리는 알킬(바람직하게는, 메틸), 알콕시(바람직하게는, 에톡시), 할로겐(바람직하게는, 클로린 또는 브로민), 또는 니트로로부터 각각 선택된 하나 이상의 치환기를 선택적으로 갖는 것을 특징으로 하는 전계발광 소자.
  3. 제1항에 있어서, 상기 얇고 조밀한 중합체 필름은 10내지 5범위의 두께를 갖는 것을 특징으로 하는 전계발광 소자.
  4. 제1항에 있어서, 상기 공액 중합체는 1eV 내지 3.5eV 범위의 반도체 대역갭을 갖는 것을 특징으로 하는 전계발광 소자.
  5. 제1항 내지 제4항중 어느 한 항에 있어서, 상기 제1전하 주입 접촉층이 알루미늄으로 된 얇은 층이고, 그 한 표면이 얇은 산화층으로 형성되고, 반도체층의 제1표면이 상기 산화층과 접촉하는것을 특징으로 하는 전계발광 소자.
  6. 제1항 내지 제4항중 어느 한 항에 있어서, 상기 제1접촉층은 마그네슘 및 은의 합금 혹은 알루미늄으로 구성된 군에서 선택되는 것을 특징으로 하는 전계발광 소자.
  7. 제5항에 있어서, 상기 제2전하 주입 접촉층은 알루미늄 및 금으로 구성된 군에서 선택되는 것을 특징으로 하는 전계발광 소자.
  8. 제1항 내지 제4항중 어느 한 항에 있어서, 상기 제1 및 제2전하 주입 접촉층의 하나 또는 양자모두는 반투명 또는 투명한 것을 특징으로 하는 전계발광 소자.
  9. 제6항에 있어서, 상기 제2접촉층은 산화인듐 또는 인듐주석산화물로 구성되는 것을 특징으로 하는 전계발광 소자.
  10. 제1항 내지 제4항중 어느 한 항에 있어서, 상기 제1접촉층은 비결정 실리콘으로 이루어지고, 상기 제2접촉층은 알루미늄, 금 및 산화인듐으로 구성된 군에서 선택되는 것을 특징으로 하는 전계발광 소자.
  11. 제1항 내지 제4항중 어느 한 항에 있어서, 상기 제1 및 제2전하 주입 접촉층의 하나 또는 양자 모두가 또한 지지 기판과 접촉하는 것을 특징으로 하는 전게발광 소자.
  12. 제11항에 있어서, 상기 지지 기판은 실리카 유리인 것을 특징으로 하는 전계발광 소자.
  13. 제11항에 있어서, 상기 지지 기판은 유연한 투명성 중합체인 것을 특징으로 하는 전계발광 소자.
  14. 제1항 내지 제13항중 어느 한 항의 전계발광 소자의 어레이(array)로서, 상기 제1 및 제2전하주입 접촉층은 상기 어레이내에 선택적으로 어드레싱하도록 배치되는 것을 특징으로 하는 전계발광 소자의 어레이.
  15. 제1 및 제2접촉층 사이에 발광 중합체의 층을 제공하는 단계를 포함하는 제1항에 따른 전계발광 소자의 제조 방법으로서, 상기 제1접촉층은 상기 소자에 대한 전기장의 인가로 제1타입의 전하 캐리어가 발광층으로 주입되도록 선택되는 전계발광소자 제조방법에 있어서, 상기 제1접촉층 및 제2접촉층중 하나를 기판상에 증착시키는 단계, 중합체 필름으로서 전구 중합체의 층을 상기 접촉층상에 증착시켜, 반도체 공액 중합체로서 발광층을 형성하도록 고온으로 증착된 전구 중합체를 가열하는 단계와, 상기 제1 및 제2접촉층중 나머지 하나를 제공하는 단계를 포함하는데, 상기 제2접촉층은, 상기 소자에 전기장을 인가함과 동시에, 제2타입의 전하 캐리어가 발광층으로 주입되도록 선택되어 배치되고, 상기 반도체 공액 중합체는, 제1접촉층에 대해 제2접촉층을 양(+)으로 되게 하도록 반도체층에 걸친 제1 및 제2접촉층사이에 전기장을 인가함과 동시에 상기 제1 및 제2타입의 전하 캐리어가 반도체층으로 주입되어지고, 상기 공액 중합체로부터 방사가 방출되도록 공액 중합체내에 방사상 붕괴하는 전하 캐리어 쌍을 형성하도록 조합하는 외이성 전하 캐리어의 저집중도를 가지는 것을 특징으로 하는 전계발광 소자 제조 방법.
  16. 제15항에 있어서, 상기 제1전하 주입 접촉층으로 얇고 조밀한 중합체 필름으로서 전구 중합체를 증착시키는 단계이전에, 합성 기판을 형성하도록 기판상에 제1전하 주입 접촉층을 먼저 증착시키는 단계를 포함하는 것을 특징으로 하는 전계발광 소자 제조 방법.
  17. 제15항 또는 제16항에 있어서, 전구 중합체는 가용성이고, 스핀식 코팅에 의해 기판상에 얇은 중합체 필름으로서 증착되는 것을 특징으로 하는 전계발광 소자 제조 방법.
  18. 제15항 또는 제16항에 있어서, 저구 중합체는 폴리(p-페닐렌비닐렌)[PPV]에 대한 전구 중합체인 것을 특징으로 하는 전계발광 소자 제조 방법.
  19. 제15항 또는 제16항에 있어서, 얇고 조밀한 중합체 필름은 10내지 5범위의 두께를 갖는 것을 특징으로 하는 전계발광 소자 제조 방법.
  20. 제15항 또는 제16항에 있어서, 제1전하 주입 접촉층이 알루미늄으로 된 얇은 층이고, 그 한 표면이 얇은 산화층으로 형성되고, 제1전하 주입 접촉층의 얇은 산화층이 반도체층과 접촉되어 있는 것을 특징으로 하는 전계발광 소자 제조 방법.
  21. 제15항 또는 제16항에 있어서, 제2전하 주입 접촉층이 알루미늄 및 금으로 구성된 군에서 선택되는 것을 특징으로 하는 전계발광 소자 제조 방법.
  22. 제16항에 있어서, 제1접촉층이 알루미늄과 마그네슘/은 합금으로 구성된 군에서 선택되고, 제2접촉층이 산화인듐인 것을 특징으로 하는 전계발광 소자 제조 방법.
  23. 제15항 또는 제16항에 있어서, 제1접촉층은 비결정 실리콘으로 이루어지고, 제2접촉층은 알루미늄, 금 및 산화인듐으로 구성된 군에서 선택되는 것을 특징으로 하는 전계발광 소자 제조 방법.
  24. 제15항 또는 제16항에 있어서, 제1 및 제2전하 주입 접촉층은 진공증착법에 의해 증착되는 것을 특징으로 하는 전계발광 소자 제조 방법.
  25. 제15항 또는 제16항에 있어서, 지지 기판은 실리카 유리인 것을 특징으로 하는 전계발광 소자 제조 방법.
  26. 제15항 또는 제16항에 있어서, 지지 기판은 유연한 투명성 중합체인 것을 특징으로 하는 전계발광 소자 제조 방법.
KR1019900702649A 1989-04-20 1990-04-18 전계발광 소자 KR100189398B1 (ko)

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PCT/GB1990/000584 WO1990013148A1 (en) 1989-04-20 1990-04-18 Electroluminescent devices

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