Efficient Triplet-triplet Annihilation-based Upconversion in Vegetable Oils

식물성 오일에서 구현되는 삼중항-삼중항 소멸법에 의한 Upconversion 분석

  • Shin, Sung Ju (Department of Chemical and Environmental Engineering, Pusan National University) ;
  • Choe, Hyun Seok (Department of Chemical and Environmental Engineering, Pusan National University) ;
  • Park, Eun-Kyoung (Department of Chemical and Environmental Engineering, Pusan National University) ;
  • Kyu, Hyun (Department of Chemical and Environmental Engineering, Pusan National University) ;
  • Han, Sangil (Department of Chemical Engineering, Changwon National University) ;
  • Kim, Jae Hyuk (Department of Chemical and Environmental Engineering, Pusan National University)
  • 신성주 (부산대학교 화공생명.환경공학부) ;
  • 최현석 (부산대학교 화공생명.환경공학부) ;
  • 박은경 (부산대학교 화공생명.환경공학부) ;
  • 현규 (부산대학교 화공생명.환경공학부) ;
  • 한상일 (창원대학교 화공시스템공학과) ;
  • 김재혁 (부산대학교 화공생명.환경공학부)
  • Received : 2016.11.09
  • Accepted : 2016.11.23
  • Published : 2016.12.10


We herein report efficient triplet-triplet annihilation upconversion (TTA-UC) achieved in various non-toxic and non-volatile vegetable oils as a UC media using platinum-octaethylporphyrin (PtOEP) and 9,10-diphenylanthracene (DPA) as a sensitizer and acceptor, respectively. Green-to-blue UC was readily achieved from PtOEP/DPA solution in vegetable oils with the quantum yield of 8% without any deoxygenation process. The UC efficiency was found to be significantly dependent on the contents of unsaturated hydrocarbon in vegetable oils and viscosity of the solution, as well. Though the Stern-volmer constant and quantum yield in vegetable oils were measured to be lower than those measured in the deaerated organic solvent, the quenching efficiency was still high enough to be 93%. In the sunflower oil, the UC threshold intensity ($I_{th}$) was approx. $100mW/cm^2$, which is far larger than the sunlight intensity, but we believe that the UC achieved in non-toxic and air-saturated media was still highly applicable to nontraditional visualization techniques such as bioimaging.


upconversion;vegetable oils;anti-stokes emission;triplett-triplet annihilation


Supported by : 부산대학교


  1. Q. Liu, B. R. Yin, T. Yang, Y. Yang, Z. Shen, P. Yao, and F. Li, A general strategy for biocompatible, high-effective upconver-sion nanocapsules based on triplet-triplet annihilation, J. Am. Chem. Soc., 135, 5029-5037 (2013).
  2. T. F. Schulze, J. Czolk, Y. Cheng, B. Fuckel, R. W. MacQueen, T. Khoury, M. J. Crossley, B. Stannowski, K. Lips, U. Lemmer, A. Colsmann, and T. W. Schmidt, Efficiency enhancement of organic and thin-film silicon solar cells with photochemical upconversion, J. Phys. Chem. C, 116, 22794-22801 (2012).
  3. T. F. Schulze and T. W. Schmidt, Photochemical upconversion: present status and prospects for its application to solar energy conversion, Energy Environ. Sci., 8, 103-125 (2015).
  4. T. N. Singh-Rachford and F. N. Castellano, Photon upconversion based on sensitized triplet-triplet annihilation, Coord. Chem. Rev., 254, 2560-2573 (2010).
  5. R. R. Islangulov, D. V. Kozlov, and F. N. Castellano, Low power upconversion using MLCT sensitizers, Chem. Commun., 30, 3776-3778 (2005).
  6. W. Zhao and F. N. Castellano, Upconverted emission from pyrene and di-tert-butylpyrene using $Ir(ppy)_3$ as triplet sensitizer, J. Phys. Chem. A, 110, 11440-11445 (2006).
  7. T. N. Singh-Rachford, A. Haefele, R. Ziessel, and F. N. Castellano, Boron dipyrromethene chromophores: next generation triplet acceptors/annihilators for low power upconversion schemes, J. Am. Chem. Soc., 130, 16164-16165 (2008).
  8. J. H. Kim, F. Deng, F. N. Castellano, and J. H. Kim, High efficiency low-power upconverting soft materials, Chem. Mater., 24, 2250-2252 (2012).
  9. J. H. Kim and J. H. Kim, Triple-emulsion microcapsules for highly efficient multispectral upconversion in the aqueous phase, ACS Photonics, 2, 633-638 (2015).
  10. A. Monguzzi, F. Bianchi, A. Bianchi, M. Mauri, R. Simonutti, R. Ruffo, R. Tubino, and F. Meinardi, High efficiency up-converting single phase elastomers for photon managing applications, Adv. Energy Mater., 3, 680-686 (2013).
  11. J. Peng, X. Guo, X. Jiang, D. Zhao, and Y. Ma, Developing efficient heavy-atom-free photosensitizers applicable to TTA upconversion in polymer films, Chem. Sci., 7, 1233-1237 (2016).
  12. P. B. Merkel and J. P. Dinnocenzo, Low-power green-to-blue and blue-to-UV upconversion in rigid polymer films, J. Lumin., 129, 303-306 (2009).
  13. M. Penconi, F. Ortica, F. Elisei, and P. L. Gentili, New molecular pairs for low power non-coherent triplet-triplet annihilation based upconversion: dependence on the triplet energies of sensitizer and emitter, J. Lumin., 135, 265-270 (2013).
  14. T. Ogawa, N. Yanai, A. Monguzzi, and N. Kimizuka, Highly efficient photon upconversion in self-assembled light-harvesting molecular systems, Sci. Rep., 5, 10882 (2015).
  15. J. H. Kim and J. H. Kim, Encapsulated triplet-triplet annihilation- based upconversion in the aqueous phase for sub-band-gap semiconductor photocatalysis, J. Am. Chem. Soc., 134, 17478-17481 (2012).