고분자 박막 내에 담지 된 실리카 마이크로입자의 광산란 효과에 의한 광에너지 상향전환 효율 향상

최현석; 이학래; 이명수; 박정민; 김재혁; Hyun-Seok Choe; Hak-Lae Lee; Myung-Soo Lee; Jeong-Min Park; Jae-Hyuk Kim

Applied Chemistry for Engineering, Vol.30, No.1, 88-94, February, 2019

DOI10.14478/ace.2018.1114 Export Citation

고분자 박막 내에 담지 된 실리카 마이크로입자의 광산란 효과에 의한 광에너지 상향전환 효율 향상

Light Scattering-enhanced Upconversion Efficiency in Silica Microparticles-embedded Polymeric Thin Film

최현석, 이학래, 이명수, 박정민, 김재혁^†

부산대학교 사회환경시스템공학과

Hyun-Seok Choe, Hak-Lae Lee, Myung-Soo Lee, Jeong-Min Park, and Jae-Hyuk Kim^†

Department of Civil and Environmental Engineering, Pusan National University, 2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan 46241, Korea

E-mail:

초록

삼중항-삼중항 소멸에 의한 광에너지 상향전환 기술(triplet-triplet annihilation upconversion, TTA-UC)은 특정 조건을 만족시키는 유기물들의 에너지 전달 및 융합 과정에 의해 저에너지의 광자를 고에너지의 광자로 변환시키는 신개념에너지 전환기술이다. 본 연구에서는 실리카 마이크로입자(silica microparticle, SM)를 UC가 구현되는 폴리우레탄 박막내에 담지 시켜 입사되는 광원의 광산란 효과를 도모함으로써 TTA-UC 효율을 향상시키고, 그 기작에 대해 탐구하였다. Seeded growth method를 통하여 약 950 nm의 균일한 크기를 갖는 SM을 합성하였으며, UC 박막 내에 담지 된 SM의 농도를 증가시킴에 따라 635 nm 광원 조사 시 430-570 nm 영역에서의 UC 세기가 최대 1.64배 증가함을 확인하였다. 삼중항 lifetime 측정을 통하여 광감응제 PdTPBP와 전자수용체 perylene 간의 triplet-triplet energy transfer(TTET) 효율을 분석한 결과, 박막 내에 담지 된 SM이 chromophore 간의 TTET에 미치는 영향은 미미한 것으로 나타났다. 또한, 입사 강도-UC 세기의 상관관계를 분석하여 TTA-UC 효율을 분석한 결과, SM이 박막 내에 존재할 경우 UC 양자효율이 최대 1.5배 향상됨을 확인하였다.

Triplet-triplet annihilation upconversion (TTA-UC) is a photochemical process wherein two or more low-energy photons are converted to a high-energy photon through a special energy transfer mechanism. Herein, we report a strategy to enhance the efficiency of TTA-UC through the light-scattering effect induced by silica microparticles (SM) embedded in polymeric thin films. By incorporating monodisperse uniform silica microparticles with a uniform size of 950 nm synthesized by Stober-based seeded growth method into UC polymeric thin films, the UC intensity in the 430-570 nm range was enhanced by as much as 64% when irradiated by 635 nm laser. Analyzing the lifetime of PdTPBP phosphorescence revealed that the presence of SM in the UC layer does not affect triplet-triplet energy transfer (TTET) between sensitizers and acceptors, supporting the enhancement of TTA-UC originated from the light-scattering effect. On the other hand, the incorporation of SM in UC layer is shown to enhance the triplet-triplet annihilation (TTA) efficiency, which results in a 1.5-fold increase of the ΦUC, by scattering light source and thus increasing the number of excited photons to be utilized in TTA-UC process.

Keywords:Silica microparticles;Seeded growth;Triplet-triplet annihilation;Upconversion;Polymeric thin film

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[1] Hill SP, Hanson K, J. Am. Chem. Soc., 139(32), 10988 (2017)

[2] Kim HI, Weon S, Kang H, Hagstrom AL, Kwon OS, Lee YS, Choi W, Kim JH, Environ. Sci. Technol., 50, 11184 (2016)

[3] Liu Q, Xu M, Yang T, Tian B, Zhang X, Li F, ACS Appl. Mater. Interfaces, 10, 9883 (2018)

[4] Huang L, Zhao Y, Zhang H, Huang K, Yang J, Han G, Angew. Chem.-Int. Edit., 56, 14400 (2017)

[5] Singh-Rachford TN, Castellano FN, Coord. Chem. Rev., 254, 2560 (2010)

[6] Sasaki Y, Amemori S, Kouno H, Yanai N, Kimizuka N, J. Mater. Chem. C, 5, 5063 (2017)

[7] Yakutkin V, Aleshchenkov S, Chernov S, Miteva T, Nelles G, Cheprakov A, Baluschev S, Chem. Eur. J., 14, 9846 (2008)

[8] Mase K, Sasaki Y, Sagara Y, Tamaoki N, Weder C, Yanai N, Kimizuka N, Angew. Chem.-Int. Edit., 57, 2806 (2018)

[9] Qu Z, Duan P, Zhou J, Wang Y, Liu M, Nanoscale, 10, 985 (2018)

[10] Singh-Rachford TN, Castellano FN, J. Phys. Chem. A, 113(20), 5912 (2009)

[11] Yanai N, Kozue M, Amemori S, Kabe R, Adachi C, Kimizuka N, J. Mater. Chem. C, 4, 6447 (2016)

[12] Meinardi F, Ehrenberg S, Dhamo L, Carulli F, Mauri M, Bruni F, Simonutti R, Kortshagen U, Brovelli S, Nat. Photonics, 11, 177 (2017)

[13] Ahn JB, Noh ST, J. Korean Ind. Eng. Chem., 19(6), 685 (2008)

[14] Fu YH, Kuznetsov AI, Miroshnichenko AE, Yu YF, Luk’yanchuk B, Nat. Commun., 4, 1527 (2013)

[15] Tsutsui T, Yahiro M, Yokogawa H, Kawano K, Adv. Mater., 13(15), 1149 (2001)

[16] Yamasaki T, Sumioka K, Tsutsui T, Appl. Phys. Lett., 76, 1243 (2000)

[17] Tao R, Zhao J, Zhong F, Zhang C, Yang W, Xu K, Chem. Commun., 51, 12403 (2015)

[18] Han YD, Lu ZY, Teng ZG, Liang JL, Guo ZL, Wang DY, Han MY, Yang WS, Langmuir, 33(23), 5879 (2017)

[19] Stober W, Fink A, Bohn E, J. Colloid Interface Sci., 26, 62 (1968)

[20] Zhao B, Tian C, Zhang Y, Tang T, Wang F, Particuology, 9, 314 (2011)

[21] Lee SH, Ayer MA, Vadrucci R, Weder C, Simon YC, Polym. Chem., 5, 6898 (2014)

[22] Hagstrom AL, Lee HL, Lee MS, Choe HS, Jung J, Park BG, Han WS, Ko JS, Kim JH, Kim JH, ACS Appl. Mater. Interfaces, 10, 8985 (2018)

[23] Ogawa T, Hosoyamada M, Yurash B, Nguyen TQ, Yanai N, Kimizuka N, J. Am. Chem. Soc., 140(28), 8788 (2018)