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1 Journal of the Korean Ceramic Society Vol. 46, No. 3, pp. 317~3, 009. DOI: /KCERS Fabrication and Optical Properties of Inorganic Electroluminescent Devices Jun-Young Lee and Jinha Hwang Department of Materials Science and Engineering, Hongik University, Seoul , Korea (Received March 10, 009; Accepted March 17, 009)» Ÿ v Ÿw p Áy w y w œw ( ; ) ABSTRACT Statistical designs of experiments were applied in order to understand the effect of processing variables on the brightness of inorganic electroluminescent displays. The main effects and interaction of phosphor and dielectric layers are estimated to be statistically significant. Additional improvement was made on removing the pores in the thick films, using the defoaming in pastes and cold isostatic pressing in bonding the top and bottom parts of the inorganic electroluminescent devices. Such optimization contributed to the reduction in the corresponding threshold voltage and enhancement in the brightness. Key words : Inorganic electroluminescent displays, Brightness, Phosphors, Dielectrics 1. v TFT-LCD (Thin Film Transistor Liquid Crystal Displays) TV, PDP (Plasma Display Panel) TV,» Ÿ v (OLED; Organic Light-Emitting Diodes) v š» wš. TV ù»» w v w»y v kw. v Ÿ (Electro-luminescence) v» Ÿ v ù w wš» Ÿ v w ƒwš.» Ÿ v 1)» Ÿ v w ƒ š k»z œw. -6)» Ÿ v y { ƒ Ÿ š,. x» Ÿ v w ƒ Corresponding author : Jinha Hwang jhwang@hongik.ac.kr Tel : Fax : w š y. w xk» Ÿ v v p w w. 1)» z x» Ÿ v (rear electrode) ù k w.,» p wù Ÿ w x w, k w p w w v w»ƒ., (front electrode) ITO (indium tin oxide) n w œ ywš Ÿ { p w z x» Ÿ xw. )» z x» Ÿ Ÿ w LCD p ƒ w ù, Ÿ (lithography) œ v w Ÿ p d wš (passive matrix driving) v ƒ. 3) z x» Ÿ v w œ x Ÿ z œ w x w ywš, w v w œ š ww. 317

2 318 Áy w Table 1. Experimental Design of Experiments for the Luminance of the Inorganic Electroluminescent Displays (Processing Variables; Thickness of a Phosphor Layer, Thickness of a Dielectric Layer, Annealing Temperature, and Annealing Time) Fig. 1. Mask design for the micropatterning for inorganic electroluminescent displays. (line width is 500 µ ). x.1. Ÿx» Ÿ»q 1,000 Å Ì ITOƒ w»q w. t w» wš ITO w (adhesion)» w»q w.»q»k» w» w m, k q w š ƒ l w.»q ITO qlyw» w Ÿ œ w.»» Ÿ ql n»q w, œ yƒ w z Ÿ ql w, w ql Fig. 1 ùkü. ITO»q Positive PR(Photo resistive film) AZP151 v gl w sw z ƒ» z j r wš Ÿ» v w Ÿw. x Ÿ PR wš ITO ƒ (etching solution) w ql ITO ƒw. PR Ÿd w. ITO ql x»q j d x w. r p(elpd-110b, ELK Corp.) ƒ 5000~7000 cp s (polymer resine) BaTiO 3 k. w d w ƒ j» w 10 o C ww. ƒ xÿ w ƒ ƒw ù 1z x Ÿ d É Ì š x w Ÿ ³. Run Order Phosphor Layer Dielectric Layer Annealing Temp. xÿ û xÿ r p w. ƒ 8000~9000 cp ûš en» w g q ZnS:Cu, Cl xÿ (ELPP-00, ELK Corp.), r p(elpp-030, ELK Corp.), Ÿ xÿ (ELPP-040, ELK Corp.) ƒƒ w. gq z w» w w. wq d xÿ d¾ w š q xÿ w /wq w k w...» Ÿ d sƒ FE-SEM (Field Emission Scanning Electron Microscopy, JSM-6700F, JEOL) w xÿ t Ì w.» š e (PDS-3000, Future Technology Laboratory) w q y j» Ÿ v Ÿ g. q w { (CS-00, KONICA MINOLTA) w { t d w. 3. m Annealing Luminance Time (cd/ ) Ÿx» Ÿ v x k (carbon) r pù (silver) r p w» z x» Ÿ l (front electrode) z (rare electrode) ITO w œ y g. ITO xÿd w Ÿ p w. d w wz

3 » Ÿ v Ÿw p 319 Fig.. Normal probability plot of luminance of the electroluminescent displays with regard to experimental variables listed in Table 1. Fig. 4. Main effecfs plot for luminance in the inorganic electroluminescent displays. Fig. 3. Pareto chart for luminance in the inorganic electroluminescent device. Ì xÿ Ì, š { e w» w x z w ww Table. 1 ùkü. 7) xÿ Ì 1z wq w,»œ j z z w w. Fig. z x» Ÿ v { p e» w ³ y. xÿ d Ì d Ì, š y ƒ ³ s j ù { w e. Pareto Chart mw mw { e ƒ w Fig y w, xÿ ̃ ƒ j w eš. d xÿd y, d ̃ { ƒ j w öeš y w. Fig. 4 (level) ƒw { y ùkü. ƒ ƒ Fig. 5. Interaction plot for luminance in the inorganic electroluminescent displays. ƒ { w. xÿ d Ÿp w w e, xÿ d ̃ ƒw xÿ ƒ ƒwš, { ƒ w» j»ƒ w». d ̃ ƒw ƒ w» ƒ» j» w { ƒ w. w j { w y w. x z w ww ww, xÿ d wš 10 o C 30 w» Ÿ { ƒ ƒ w ùkû. Fig. 5 y xÿd d ̃ 0.05 ƒ y y w. j xÿ d t x w, xÿ ³ w s. xÿ j» 10~0 µm š 1µm w w ùkû. ƒ Ÿ 46«3y(009)

4 이준영 황진하 30 Fig. 6. Fig. 7. Luminance characteristics of inorganic electroluminescent displays fabricated using screen printing. Fig. 8. Luminance characteristics after cold isostatic pressing was applied upon bonding the top and bottom parts of the inorganic electroluminescent devices. Images (a) before and (b) after illumination in inorganic electroluminescent displays.(no pressure was applied to bonding of the top and bottom substrates) 하다고 결정된 소자의 발광 특성을 휘도계를 사용하여 측 정한 결과를 Fig. 6에 도시하였다. Fig. 6에서와 같이 아 무런 처리 없이 형광체와 유전체 교반 후 직접 붙인 1인 치 청녹색 IELD소자의 경우 00 V(500 khz)의 전압이 인 가될 경우 약 70 cd/m 의 휘도를 나타내었고 색좌표(color coordination)는 x=0.1, y=0.35로 나타났다. 이는 탄소나 은 페이스트를 후면전극으로 사용한 무기 전계 발광소자의 휘도값인 50~60 cd/m 보다 우수한 것이다. 무기 전계 발 광 소자가 발광을 시작하는 기점으로 삼는 문턱전압은 일 반적으로 휘도가 1 cd/m 일 때의 전압을 말하는데 약 100 V로 측정되었다. 본 연구에서 개발한 방법은 상/하판 에 형광체를 인쇄하고 서로 접합시키기 때문에 단순접합 시에는 Fig. 7에서와 같이 소결 후 다량의 기공이 발생된다. 이러한 기공을 줄이기 위해 상/하판 유리기판의 접합시 압력을 가하는 것이 중요하다. 본 연구에서는 기존의 상 한국세라믹학회지 Fig. 9. Luminance characteristics of the inorganic electroluminescent devices optimized in terms of cold isostatic pressing and defoaming. 하판 기판을 수동으로 접합한 후에 진공 팩에 넣어 정수 압(Cold Isostatic Pressing)으로 가압할 경우, 상하판사이에 위치한 Paste의 접착력을 향상시켜, 휘도 특성을 개선시 킬 수 있다. 본 연구는 기존의 전통적인 세라믹 공정에 적용되던 정수압 공정을 후막공정에 응용한 경우이다. 압력을 가한 경우 00 V와 500 Hz의 인가전압 하에서의 휘도값은 약 10 cd/m 로 크게 증가하였다. 또한 문턱전 8)

5 무기전계발광 디스플레이 소자 제작 및 광학 특성 연구 Fig Images (a) before and (b) after illumination in the optimized inorganic electroluminescent devices. (Cold isostatic pressing and defoaming was applied upon the inorganic electroluminescent device) Fig. 1. Luminance characteristics in the inorganic electroluminescent devices as a function of type of phosphors. 4. Fig. 11. Image after illumination of the inorganic electroluminescent device patterned using photolithography. (line width= 500 µm) 압도 70 V로 감소하였다. (Fig. 8참조) 또한 기공의 존재 를 최소화하기 위해 인쇄전의 탈포 (defoaming)공정도 적 용한 결과 Fig. 9와 같은 최적의 발광 특성을 얻을 수 있 었다. 최종적으로 최적화된 무기전계 발광 소자의 제작된 모습을 Fig. 10에 보여주고 있다. 따라서 본 연구에서 최 적화된 무기전계 발광 소자의 발광 특성은 Fig. 9에 보여 진 바와 같이 문턱전압이 50 V이고 00 V (주파수는 1 khz 로 고정한 경우) 인가전압에서 휘도가 00 cd/m 로 밝기 측면에서 LCD와 비슷한 수준의 매우 우수한 무기전계 발 광 소자를 구현할 수 있었다. 위에 전술한 발광 시스템은 전면 발광 형태이지만, 상 용화를 위해서는 미세패턴의 구현이 필수적이다. 이에 본 연구는 상판과 하판의 유리기판에 증착된 투명 전극을 Fig. 1과 같이 미세패턴을 구현하여 40 40개 총 1600개 의 화소를 구현하였다. 무기 전계 발광 디스플레이 공정 은 위의 후막 공정에 투명전극의 미세패턴 형성 공정을 추가한 것으로 제작된 무기 전계 발광 소자의 발광 모습 과 발광 특성을 Fig. 11과 Fig. 1에 정리하였다. 특히 Fig. 1의 결과는 녹색, 청색, 및 주황색 형광체를 채용한 결과를 동시에 보여주고 있다. 청색 형광체가 가장 우수 한 발광 특성을 보여줌을 확인할 수 있었다. 결 론 기존의 은(Ag) 혹은 탄소 분말을 사용하여 제작된 후면 전극은 유전체와의 접합 특성이 우수하지 못하여, 발광효 율이 떨어지는 문제점을 갖고 있다. 이를 개선하기 위하 여 후면전극 역시 ITO 기반의 투명전극으로 대체하는 방 법을 고안하였으며 다음과 같은 결론을 내릴 수 있다. 후막형 무기전계발광소자의 핵심공정인 스크린 인쇄공 정 최적화를 위해 시행한 휘도에 대한 실험계획법 분석 결과로부터 형광체의 두께, 형광체와 유전체의 두께의 교 호작용, 유전체의 두께가 통계적으로 유의한 효과임을 확 인하였다. 실험계획법 분석을 바탕으로 형광체와 유전체 의 두께를 최적화하였다. 상/하판의 전극을 모두 ITO 투명전극을 사용할 경우, 높은 휘도를 나타내는 유전체와 형광층의 적정 인쇄 두 께가 존재함을 알았다. 하판 ITO 기판에 유전체와 형광체 Paste를 인쇄하고 상 부 ITO에도 형광체를 도포하여 접합시킨 무기전계 발광 소자의 경우, 페이스트 전극을 이용한 일반적인 기존 소 자의 휘도에 비해 우수한 발광 특성을 나타내었으며 이 는 유전체와의 접합 특성이 탄소나 은 페이스트에 비해 ITO 전극이 우수하기 때문인 것으로 추정된다. 상/하판 접합 후 열처리 시, 소자에 압력을 가하고 형 광체를 인쇄 전에 탈포할 경우, 휘도가 약 경우 약 1.7배 정도 증가함을 알 수 있었는데 열처리시 형광체에 포함 된 용매와 교반시 형광체 내부에 생성되는 기공을 제거 하는 것이 접합 후 기공결함 감소와 발광효율 증가 효과 제 46 권 제 3호(009)

6 3 Áy w wì w. Acknowledgment 006w y w w w. REFERENCES 1. Yoshimasa A. Ono, Electroluminescent Displays, pp.1-6, World Scientific. Publishing Co. Pte. Ltd., Singapore, A. G. Fischer, Electroluminescent Lines in ZnS Powder Particles, J. Electrochem. Soc., 109 [11] (196) 3. A. G. Fischer, Electroluminescent Lines in ZnS Powder Particles, J. Electrochem. Soc., 110 [7] (1963) 4. A. G. Fischer, Electroluminescent II-VI Heterojunctions, J. Electrochem. Soc., 118 [6] 139C-44C (1971) 5. C.W. Tang and S.A. VanSlyke, Organic Electroluminescent Diodes, Appl. Phys. Lett., (1987) 6. C.W. Tang, S.A. VanSlyke, and C.H. Chen, Electroluminescence of Doped Organic Thin Films, J. Appl. Phys., (1989) 7. D.C. Montgomery and G.C. Runger, Applied Statistics and Probability for Engineers, pp , John Wiley & Sons, Inc., J. S. Reeds, Principles of Ceramic Processing, pp.56-58, John Wiley & Sons, Inc., w wz

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