Suitable Polymeric Coatings to Avoid Localized Surface Plasmon Resonance Hybridization in Printed Patterns of Photothermally Responsive Gold Nanoinks

When using gold nanoparticle (AuNP) inks for writing photothermal readable secure information, it is of utmost importance to obtain a sharp and stable shape of the localized surface plasmon resonance (LSPR) absorption bands in the prints. The T increase at a given irradiation wavelength (Delta T-lambda) is the retrieved information when printed patterns are interrogated with a laser source. As Delta T-lambda is proportional to the absorbance at the wavelength lambda, any enlargement or change of the absorbance peak shape in a printed pattern would lead to wrong or unreliable reading. With the aim of preparing AuNP inks suitable for inkjet printing of patterns with stable and reliable photothermal reading, we prepared liquid solutions of spherical AuNP coated with a series of different polymers and with or without additional dispersant. The optical stability of the inks and of the printed patterns were checked by monitoring the shape changes of the sharp LSPR absorption band of AuNP in the visible (lambda (max) 519 nm) along weeks of ageing. AuNP coated with neutral polyethylenglycol thiols (HS-PEG) of mw 2000-20000 showed a strong tendency to rapidly agglomerate in the dry prints. The close contact between agglomerated AuNP resulted in the loss of the pristine shape of the LSPR band, that flattened and enlarged with the further appearance of a second maximum in the Near IR, due to plasmon hybridization. The tendency to agglomerate was found directly proportional to the PEG mw. Addition of the ethylcellulose (EC) dispersant to inks resulted in an even stronger and faster tendency to LSPR peak shape deformation in the prints due to EC hydrophobicity, that induced AuNP segregation and promoted agglomeration. The introduction of a charge on the AuNP coating revelead to be the correct way to avoid agglomeration and obtain printed patterns with a sharp LSPR absorption band, stable with ageing. While the use of a simple PEG thiol with a terminal negative charge, HS-PEGCOO(-) (mw 3000), was not sufficient, overcoating with the positively charged polyallylamine hydrochloride (PAH) and further overcoating with the negatively charged polystyrene sulfonate (PSS) yielded AuNP@HS-PEGCOO(-)/PAH(+) and AuNP@HS-PEGCOO(-)/PAH(+)/PSS(-), both giving stable prints. With these inks we have shown that it is possible to write photothermally readable secure information. In particular, the generation of reliable three-wavelength photothemal barcodes has been demonstrated.