Oxygen vacancy levels mediated photophysical pathways of NIR-II responsive broadband upconversion

Abstract

The photon upconversion (UC) is the process that has been known for a long time. Especially, lanthanide-based UC materials recently have attracted huge interest of scientific community due to their narrow visible emission bands upon near-infrared (NIR) excitation. However, the excitation in the high excitation power of NIR can cause highly bright and broad emission (B-UC). Such explosive B-UC was distinct at high excitation condition with UC wavelength encompassing the entire visible range. Previously, the proposed model of B-UC origination includes heat, multi-photon absorption, and accumulated thermal energy transfer. In this article, we will show various experimental and theoretical evidence supporting the idea that B-UC arises from photophysical pathways. Here, the key experimental evidence for photophysical pathways model of B-UC is to measure B-UC in the low-temperature environment (22 K). In addition, the density functional theory was used to regenerate energy levels which would be compared to the absorption spectral bands in Er2O3. As a result, we are confident of an electron tunneling model from P-2(3/2) of Er3+ to oxygen vacancy level (V-O) of Er2O3. Then, V-O electrons are sequentially excited to the conduction band of Er2O3 by energy transfer from F-4(9/2) of Er3+. Finally, the electrons return to the V-O of Er2O3 with concomitant B-UC. Published under an exclusive license by AIP Publishing.