Fluorine Doping Mediated Epitaxial Growth of NaREF4 on TiO2 for Boosting NIR Light Utilization in Bioimaging and Photodynamic Therapy

Author:

Kou Yufang1,Liu Minchao1,Zhou Qiaoyu1,Lin Runfeng1,Yu Hongyue1,Hou Mengmeng1,Ming Jiang1,Tang Yi1,Elzatahry Ahmed A.2,Zhang Fan1,Zhao Dongyuan1,Li Xiaomin1ORCID

Affiliation:

1. Department of Chemistry, Shanghai Stomatological Hospital & School of Stomatology, State Key Laboratory of Molecular Engineering of Polymers, iChem (Collaborative Innovation Center of Chemistry for Energy Materials), Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University Shanghai 200433 China

2. Materials Science and Technology Program, College of Arts and Sciences Qatar University, P.O. Box 2713 Doha 2713 Qatar

Abstract

AbstractBy integrating TiO2 with rare earth upconversion nanocrystals (NaREF4), efficient energy transfer can be achieved between the two subunits under near‐infrared (NIR) excitation, which hold tremendous potential in the fields of photocatalysis, photodynamic therapy (PDT), etc. However, in the previous studies, the combination of TiO2 with NaREF4 is a non‐epitaxial random blending mode, resulting in a diminished energy transfer efficiency between the NaREF4 and TiO2. Herein, we present a fluorine doping‐mediated epitaxial growth strategy for the synthesis of TiO2‐NaREF4 heteronanocrystals (HNCs). Due to the epitaxial growth connection, NaREF4 can transfer energy through phonon‐assisted pathway to TiO2, which is more efficient than the traditional indirect secondary photon excitation. Additionally, F doping brings oxygen vacancies in the TiO2 subunit, which further introduces new impurity energy levels in the intrinsic band gap of TiO2 subunit, and facilitates the energy transfer through phonon‐assisted method from NaREF4 to TiO2. As a proof of concept, TiO2‐NaGdF4 : Yb,Tm@NaYF4@NaGdF4 : Nd@NaYF4 HNCs were rationally constructed. Taking advantage of the dual‐model up‐ and downconversion luminescence of the delicately designed multi‐shell structured NaREF4 subunit, highly efficient photo‐response capability of the F‐doped TiO2 subunit and the efficient phonon‐assisted energy transfer between them, the prepared HNCs provide a distinctive nanoplatform for bioimaging‐guided NIR‐triggered PDT.

Funder

National Natural Science Foundation of China

National Key Research and Development Program of China

Fundamental Research Funds for the Central Universities

Publisher

Wiley

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