Near infrared (NIR) absorbing nanoparticles synthesized by the reduction of HAuCl4 with Na2S exhibited absorption bands at ∼530 nm, and in the NIR region of 650–1100 nm. The NIR optical properties were not found to be related to the earlier proposed Au2S–Au core-shell microstructure in previous studies. From a detailed study of the structure and microstructure of as-synthesized particles in this work, S-containing, Au-rich, multiply-twinned nanoparticles were found to exhibit NIR absorption. They consisted of amorphous AuxS (where x = 2), mostly well mixed within crystalline Au, with a small degree of surface segregation of S. Therefore, NIR absorption was likely due to interfacial effects on particle polarization from the introduction of AuxS into Au particles, and not the dielectric confinement of plasmons associated with a core-shell microstructure.
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This work was supported by the Singapore-Massachusetts Institute of Technology Alliance and National University of Singapore (NUS) Academic Research Grant. G.M. Chow acknowledges the support of the United States Office of Naval Research. The authors thank Changhai Wang, Xingyu Gao, Chengjun Sun, and Giuseppe Faraci for assistance with data collection at the synchrotron beam lines. The support of beam time from National Synchrotron Radiation Research Center (Taiwan), Singapore Synchrotron Light Source, and European Synchrotron Radiation Facility (Grenoble, France) is acknowledged. The authors thank Binghai Liu for assistance in TEM.
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Tan, M.C., Ying, J.Y. & Chow, G.M. Structure and microstructure of near infrared-absorbing Au–Au2S nanoparticles. Journal of Materials Research 22, 2531–2538 (2007). https://doi.org/10.1557/jmr.2007.0314