Anisotropic nanocluster arrays to a diminished zone: different regimes of surface deposition of gold nanocolloids

Abstract

Evaporation-induced assembly of nanoparticles has emerged as a versatile technique for the production of large-scale ordered structures and materials with complex features. In this study, we show that a dried particulate of an anisotropic nanocolloid undergoes non-ubiquitous surface morphological transitions at varying particle concentrations. Below 5 nM, deposits reveal the formation of linear arrays of AuNR clusters outside of the coffee ring and an annular CTAB-rich depletion zone in the inner vicinity of the coffee ring. For nanoparticle concentrations ≥5 nM, the outer cluster deposits disappear and a region of reduced AuNR density, sandwiched between the coffee ring and the depletion zone, analogous to the diminished zone, is observed. Within the coffee-ring deposits, nanoscale smectic AuNR assembly occurs via the expulsion of the cetyltrimethyl ammonium bromide (CTAB) bilayer, which contributes to the inward solutal Marangoni flow. An enhanced inward solutal Marangoni flow at high particle concentrations assists in the formation of a wider depletion zone, the emergence of the diminished zone and suppression of the width of the coffee-ring deposits. Through detailed analysis of data from ex situ (scanning electron microscopy, SEM) and in situ (contact angle and confocal imaging) measurements, we establish a direct correlation between the different evaporation modes and the various deposition regimes. A detailed mechanism for the surface morphology modulation of AuNR deposits by tuning the nanoparticle concentration in the drying sessile drop is discussed.