Optical nanomaterials have been widely used in anticounterfeiting applications. There have been significant developments powered by recent advances in material science, printing technologies, and the availability of smartphone-based decoding technology. Recent progress in this field is surveyed, including the availability of optical reflection, absorption, scattering, and luminescent nanoparticles. It is demonstrated that advances in the design and synthesis of lanthanide-doped upconversion nanoparticles will lead to the next generation of anticounterfeiting technologies. Their tunable optical properties and optical responses to a range of external stimuli allow high-security level information encoding. Challenges in the scale-up synthesis of nanomaterials, engineering of assessorial devices for smart-phone-based decryption, and alignment to the potential markets which will lead to new directions for research, are discussed.

Optical Nanomaterials and Enabling Technologies for High-Security-Level Anticounterfeiting.

Lanthanide-doped upconversion (UC) phosphors absorb low-energy infrared light and convert it into higher-energy visible light. Despite over 10 years of development, it has not been possible to synthesize nanocrystals (NCs) with UC efficiencies on a par with what can be achieved in bulk materials. To guide the design and realization of more efficient UC NCs, a better understanding is necessary of the loss pathways competing with UC. Here we study the excited-state dynamics of the workhorse UC material β-NaYF4 co-doped with Yb3+ and Er3+. For each of the energy levels involved in infrared-to-visible UC, we measure and model the competition between spontaneous emission, energy transfer between lanthanide ions, and other decay processes. An important quenching pathway is energy transfer to high-energy vibrations of solvent and/or ligand molecules surrounding the NCs, as evidenced by the effect of energy resonances between electronic transitions of the lanthanide ions and vibrations of the solvent molecules. We present a microscopic quantitative model for the quenching dynamics in UC NCs. It takes into account cross-relaxation at high lanthanide-doping concentration as well as Forster resonance energy transfer from lanthanide excited states to vibrational modes of molecules surrounding the UC NCs. Our model thereby provides insight in the inert-shell thickness required to prevent solvent quenching in NCs. Overall, the strongest contribution to reduced UC efficiencies in core-shell NCs comes from quenching of the near-infrared energy levels (Er3+: 4I11/2 and Yb3+: 2F5/2), which is likely due to vibrational coupling to OH- defects incorporated in the NCs during synthesis.

Quenching Pathways in NaYF4:Er3+,Yb3+ Upconversion Nanocrystals

Anti-counterfeiting patterns are encrypted with nanotaggants that are selectively excited at distinct wavelengths. Decryption is realized by examining the temporal color or graphic responses of the pattern under various illumination wavelengths. The covert color and graphic codes that are designable through control of the nanotaggant composition are expected to provide high-level security.

Anti-counterfeiting patterns encrypted with multi-mode luminescent nanotaggants.

Recent advances in upconversion nanocrystals: Expanding the kaleidoscopic toolbox for emerging applications

The modulation of luminescence is essential because unwanted spontaneous-emission modes have a negative effect on the performance of luminescence-based photonic devices. Photonic crystals are promising materials for the control of light emission because of the variation in the local density of optical modes within them. They have been widely investigated for the manipulation of the emission intensity and lifetime of light emitters. Several groups have achieved greatly enhanced emission by depositing emitters on the surface of photonic crystals. Herein, the different modulating effects of photonic crystal dimensions, light-emitter positions, photonic crystal structure type, and the refractive index of photonic crystal building blocks are highlighted, with the aim of evaluating the fundamental principles that determine light propagation. The applications of using photonic crystals to manipulate spontaneous emission in light-emitting diodes and sensors are also reviewed. In addition, potential future challenges and improvements in this field are presented.

Manipulating Luminescence of Light Emitters by Photonic Crystals.

A 2D surface plasmon photonic crystal (SPPC) is achieved by implanting gold nanorods onto the periodic surface apertures of the poly(methyl methacrylate) (PMMA) opal photonic crystals. On the surface of the SPPC, the overall upconversion luminescence intensity of NaYF4 :Yb(3+) , Er(3+) under 980 nm excitation is improved more than 10(3) fold. The device is easily shifted to a transparent flexible substrate, applied to flexible displays.

Guanshi Qin

Papers

Local Field Modulation Induced Three‐Order Upconversion Enhancement: Combining Surface Plasmon Effect and Photonic Crystal Effect