title: Formation and optical properties of fluorescent gold nanoparticles obtained by matrix sputtering method with volatile mercaptan molecules in the vacuum chamber and consideration of their structures.
abstract: This paper proposes a novel methodology to synthesize highly fluorescent gold nanoparticles (NPs) with a maximum quantum yield of 16%, in the near-infrared (IR) region. This work discusses the results of using our (previously developed) matrix sputtering method to introduce mercaptan molecules, α-thioglycerol, inside the vacuum sputtering chamber, during the synthesis of metal NPs. The evaporation of α-thioglycerol inside the chamber enables to coordinate to the "nucleation stage" very small gold nanoclusters in the gas phase, thus retaining their photophysical characteristics. As observed through transmission electron microscopy, the size of the Au NPs obtained with the addition of α-thioglycerol varied from approximately 2-3 nm to approximately 5 nm. Plasmon absorption varied with the size of the resultant nanoparticles. Thus, plasmon absorption was observed at 2.4 eV in the larger NPs. However, it was not observed, and instead a new peak was found at approximately 3.4 eV, in the smaller NPs that resulted from the introduction of α-thioglycerol. The Au NPs stabilized by the α-thioglycerol fluoresced at approximately 1.8 eV, and the maximum wavelength shifted toward the red, in accordance with the size of the NPs. A maximum fluorescent quantum yield of 16% was realized under the optimum conditions, and this value is extremely high compared to values previously reported on gold NPs and clusters (generally ∼1%). To our knowledge, however, Au NPs of size >2 nm usually do not show strong fluorescence. By comparison with results reported in previous literature, it was concluded that these highly fluorescent Au NPs consist of gold-mercaptan complexes. The novel method presented in this paper therefore opens a new door for the effective control of size, photophysical characteristics, and structure of metal NPs. It is hoped that this research contributes significantly to the science in this field.
authors.affiliation: †Division of Material Science and Engineering, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0808, Japan.
authors.forename: Taiki
authors.initials: T
authors.lastname: Sumi
authors.affiliation: †Division of Material Science and Engineering, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0808, Japan.
authors.forename: Shingo
authors.initials: S
authors.lastname: Motono
authors.affiliation: †Division of Material Science and Engineering, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0808, Japan.
authors.forename: Yohei
authors.initials: Y
authors.lastname: Ishida
authors.affiliation: ‡National Institute for Material Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
authors.forename: Naoto
authors.initials: N
authors.lastname: Shirahata
authors.affiliation: †Division of Material Science and Engineering, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0808, Japan.
authors.forename: Tetsu
authors.initials: T
authors.lastname: Yonezawa