분무열분해법으로 CeO2:Er/Yb 형광체 제조 및 발광특성 최적화

정경열; 박재훈; 송신애; Kyeong Youl Jung; Jea Hoon Park; Shin Ae Song

Applied Chemistry for Engineering, Vol.26, No.3, 319-325, June, 2015

DOI10.14478/ace.2015.1028 Export Citation

분무열분해법으로 CeO2:Er/Yb 형광체 제조 및 발광특성 최적화

Preparation and Luminescence Optimization of CeO2:Er/Yb Phosphor Prepared by Spray Pyrolysis

정경열 ^†, 박재훈, 송신애¹

공주대학교 화학공학부
¹한국생산기술연구원 마이크로제조시스템기술센터

Kyeong Youl Jung^†, Jea Hoon Park, and Shin Ae Song¹

Department of Chemical Engineering, Kongju National University, 1223-24 Cheonan-Daero, Seobuk-gu, Cheonan, Republic of Korea
¹Energy Materials Research Center, Korea Research Institute of Chemical Technology, Sinseongno 19, P.O.Box 107, Daejeon 305-600, Republic of Korea

E-mail:

초록

분무열분해법을 이용하여 서브 미크론 크기의 CeO2:Er3+/Yb3+ 상향 변환 형광체 입자를 합성하고 Er3+ 및 Yb3+ 농도변화에 따른 발광특성을 조사하였다. 합성한 CeO2:Er3+/Yb3+는 Er3+ 활성이온의 4S3/2/2H11/2 → 4I15/2 및 4F9/2 → 4I15/2 전이에 기인한 강한 녹색 및 적색 발광을 보였다. 가장 높은 발광을 보이는 활성제 농도는 Er = 1.0% 그리고 Yb = 2.0%이며, 농도소광 현상은 쌍극자-쌍극자 상호작용을 통해 일어남이 확인되었다. 레이저 다이오드 여기 광 세기에 대한 발광강도 의존성을 활성이온 농도에 따라 조사하였고, 발광 중간 에너지 레벨의 주 소멸과정을 고려하여 발광 메커니즘을 조사하였다. Yb3+에서 Er3+으로 에너지 전달은 바닥 상태 흡수(ground state absorption, GSA)에 기여하고, Yb3+ 도핑은 4I11/2 → 4I13/2 전이를 가속화시켜 적색/녹색 발광세기 비를 상승시킨다. 최종적으로 분무열분해법으로 제조된 CeO2:Er3+/Yb3+ 형광체의 발광은 선형 감쇠가 중간 에너지 레벨의 고갈을 지배하는 2 광자 프로세스에 의해 일어남을 확인하였다.

Submicron-sized CeO2:Er3+/Yb3+ upconversion phosphor particles were synthesized by spray pyrolysis, and their luminescent properties were characterized by changing the concentration of Er3+ and Yb3+. CeO2:Er3+/Yb3+ showed an intense green and red emission due to the 4S3/2 or 2H11/2 → 4I15/2 and 4F9/2 → 4I15/2 transition of Er3+ ions, respectively. In terms of the emission intensity, the optimal concentrations of Er and Yb were 1.0 % and 2.0%, respectively, and the concentration quenching was found to occur via the dipole-dipole interaction. Upconversion mechanism was discussed by using the dependency of emission intensities on pumping powers and considering the dominant depletion processes of intermediate energy levels for the red and green emission with changing the Er3+ concentration. An energy transfer from Yb3+ to Er3+ in CeO2 host was mainly involved in ground-state absorption (GSA), and non-radiative relaxation from 4I11/2 to 4I13/2 of Er3+ was accelerated by the Yb3+ co-doping. As a result, the Yb3+ co-doping led to greatly enhance the upconversion intensity with increasing ratios of the red to green emission. Finally, it is revealed that the upconversion emission is achieved by two photon processes in which the linear decay dominates the depletion of intermediate energy levels for green and red emissions for CeO2:Er3+/Yb3+ phosphor.

Keywords:Upconversion phosphor;Spray pyrolysis;Energy transfer;two-photon process

[References]

Li Q, Feng W, Li F, Coord. Chem. Rev., 273, 100 (2014)
Hinklin TR, Rand SC, Laine RM, Adv. Mater., 20(7), 1270 (2008)
Meruga JM, Baride A, Cross W, Keller JJ, May PS, J. Mater. Chem. C, 2, 2221 (2014)
Song EH, Ding S, Wu M, Ye S, Chen ZT, Ma YY, Zhang QY, Opt. Mater. Express, 4, 1186 (2014)
Lim MJ, Ko YN, Kang YC, Jung KY, RSC Adv., 4, 10039 (2014)
He M, Huang P, Zhang C, Ma J, He R, Cui D, Chem. Eur. J., 18, 5954 (2012)
Ding M, Chen D, Chen T, Lu C, Ni Y, Xu Z, Mater. Lett., 128, 101 (2014)
Song Y, Huang Y, Zhang L, Zheng Y, Guo N, You H, RSC Adv., 2, 4777 (2012)
Vetrone F, Boyer JC, Capobianoco JA, Speghini A, Bettinelli M, Chem. Mater., 15, 2737 (2013)
Zeng JH, Su J, Li ZH, Yan RX, Li YD, Adv. Mater., 14, 2119 (2005)
Mi CC, Tian ZH, Cao C, Wang ZJ, Mao CB, Xu SK, Langmuir, 27(23), 14632 (2011)
Zhao J, Lu Z, Yin Y, Mcrae C, Piper JA, Dawes JM, Jin D, Goldys EM, Nanoscale, 5, 944 (2013)
Haase M, Schafer H, Angew. Chem.-Int. Edit., 50, 5808 (2011)
Liu X, Zhang X, Tian G, Yin W, Yan L, Ruan L, Yang Z, Xiao D, Gu Z, Cryst. Eng. Comm., 16, 5650 (2014)
Xiao QL, Dong GP, Qiu JR, J. Am. Ceram. Soc., 97(6), 1899 (2014)
Vetrone F, Boyer JC, Capobianco JA, Speghini A, Bettinelli M, J. Phys. Chem. B, 107(5), 1107 (2003)
Matsuura D, Hattori H, Takano A, J. Electrochem. Soc., 152(3), H39 (2005)
Dwivedi Y, Bahadur A, Rai SB, J. Appl. Phys., 110, 043103 (2011)
Singh V, Rai VK, Al-Shamery K, Haase M, Kim SH, Appl. Phys. A-Mater. Sci. Process., 113, 747 (2013)
Zheng K, Song W, Lv C, Liu Z, Qin W, Cryst. Eng. Comm., 16, 4329 (2014)
Yang J, Lin J, J. Electrochem. Soc., 157(12), K273 (2010)
Xu Z, Zhao Q, Sun Y, Ren B, You L, Wang S, Ding F, RSC Adv., 3, 8407 (2013)
Liu X, Chen S, Wang X, J. Lumin., 127, 650 (2007)
Cho JH, Bass M, Babu S, Dowding JM, Self WT, Seal S, J. Lumin., 132, 743 (2012)
Wang ZY, Gu FB, Wang ZH, Han DM, Mater. Res. Bull., 53, 141 (2014)
Jung KY, Lee HW, Kang YC, Park SB, Yang YS, Chem. Mater., 17, 2729 (2005)
Maniquiz MC, Jung KY, Jeong SM, J. Electrochem. Soc., 157, H1135 (2010)
Kim JH, Jung KY, J. Lumin., 132, 1376 (2012)
Chung W, Yu HJ, Park SH, Chun BH, Kim J, Kim SH, J. Cryst. Growth, 326(1), 73 (2011)
Kim JH, Jung KY, J. Lumin., 131, 1487 (2011)
Dexter DL, J. Chem. Phys., 31, 836 (1953)
Poort SHM, Blocpoel WP, Blasse G, Chem. Mater., 7, 1547 (1995)
Lei Y, Song H, Yang L, Yu L, Liu Z, Pan G, Bai X, Fan L, J. Chem. Phys., 123, 174710 (2005)

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