Stable Inks Containing Upconverting Nanoparticles Based on an Oil-in-Water Nanoemulsion.

An oil-in-water nanoemulsion capable of dispersing upconverting nanoparticles (UCNPs) for 7 months was investigated. Negative staining transmission electron microscopy shows that the UCNPs reside in the oil phase of the nanoemulsion. Dynamic light scattering measurements indicate that the majority of the oil volume is contained in droplets less than 1 µm in diameter. The system studied could be used to inkjet print UCNPs at least 7 months after the ink was first formulated. Nanoemulsion stability was tested in the short term, over 11 days, using an ink stability test developed for this research. It was found that after an initial loss of UCNPs, the majority of the UCNPs remained well-dispersed in solution. The UCNP dispersion was stable for longer periods under storage at 333 K compared to storage at 277 K.

Hansen solubility parameters of surfactant-capped silver nanoparticles for ink and printing technologies.

Optimal ink formulations, inclusive of nanoparticles, are often limited to matching the nanoparticle's capping agent or surface degree of polarity to the solvent of choice. Rather than relying on this single attribute, nanoparticle dispersibility was optimized by identifying the Hansen solubility parameters (HSPs) of decanoic-acid-capped 5 nm silver nanoparticles (AgNPs) by broad spectrum dispersion testing and a more specific binary solvent gradient dispersion method. From the HSPs, solvents were chosen to disperse poly(methyl methacrylate) (PMMA) and nanoparticles, give uniform evaporation profiles, and yield a phase-separated microstructure of nanoparticles on PMMA via film formation by solvent evaporation. The goal of this research was to yield a film that is reflective or transparent depending on the angle of incident light (i.e., optically variable). The nanoparticle HSPs were very close to alkanes with added small polar and hydrogen-bonding components. This led to two ink formulations: one of 90:10 vol % toluene/methyl benzoate and one containing 80:10:10 vol % toluene/p-xylene/mesitylene, both of which yielded the desired final microstructure of a nanoparticle layer on a PMMA film. This approach to nanoparticle ink formulation allows one to obtain an ink that has desirable dispersive qualities, rheology, and evaporation to give a desired printed structure.

Security printing of covert quick response codes using upconverting nanoparticle inks.

Counterfeiting costs governments and private industries billions of dollars annually due to loss of value in currency and other printed items. This research involves using lanthanide doped ß-NaYF(4) nanoparticles for security printing applications. Inks comprised of Yb(3+)/Er(3+) and Yb(3+)/Tm(3+) doped ß-NaYF(4) nanoparticles with oleic acid as the capping agent in toluene and methyl benzoate with poly(methyl methacrylate) (PMMA) as the binding agent were used to print quick response (QR) codes. The QR codes were made using an AutoCAD file and printed with Optomec direct-write aerosol jetting(®). The printed QR codes are invisible under ambient lighting conditions, but are readable using a near-IR laser, and were successfully scanned using a smart phone. This research demonstrates that QR codes, which have been used primarily for information sharing applications, can also be used for security purposes. Higher levels of security were achieved by printing both green and blue upconverting inks, based on combinations of Er(3+)/Yb(3+) and Tm(3+)/Yb(3+), respectively, in a single QR code. The near-infrared (NIR)-to-visible upconversion luminescence properties of the two-ink QR codes were analyzed, including the influence of NIR excitation power density on perceived color, in term of the CIE 1931 chromaticity index. It was also shown that this security ink can be optimized for line width, thickness and stability on different substrates.

Patterned direct-write and screen-printing of NIR-to-visible upconverting inks for security applications.

Two methods of direct-write printing for producing highly resolved features of a polymer impregnated with luminescent upconversion phosphors for security applications are presented. The printed polymer structures range in shape from features to text. The thin polymer features were deposited by direct-write printing of atomized material as well as by screen-printing techniques. These films contain highly luminescent lanthanide-doped, rare-earth nanocrystals, ß-NaYF4:3%Er, 17%Yb, which are capped with oleic acid. This capping agent allows the nanocrystals to disperse throughout the films for full detailing of printed features. Upconversion of deposited features was obtained using a 980 nm wavelength laser with emission of upconverted light in the visible region at both 540 and 660 nm. Features were deposited onto high bond paper, Kapton®, and glass to demonstrate possible covert and forensic security printing applications, as they are printed in various features and invisible to 'naked-eye' viewing at low concentrations of nanocrystals.