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Article

Spontaneous Shape Alteration and Size Separation of Surfactant-Free Silver Particles Synthesized by Laser Ablation in Acetone during Long-Period Storage

1
RIKEN Center for Advanced Photonics, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
2
Department of Nano-Mechatronics, Korea University of Science and Technology (UST), 217 Gajeong-Ro, Yuseong-Gu, Daejeon 34113, Korea
3
Department of Nano-Manufacturing Technology, Korea Institute of Machinery and Material (KIMM), 156 Gajeongbuk-Ro, Yuseong-Gu, Daejeon 34103, Korea
4
Technical Chemistry I and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Universitaetsstrasse 7, 45141 Essen, Germany
5
Department of Laser & Electron Beam Application, Korea Institute of Machinery and Material (KIMM), 156 Gajeongbuk-Ro, Yuseong-Gu, Daejeon 34103, Korea
*
Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Nanomaterials 2018, 8(7), 529; https://doi.org/10.3390/nano8070529
Received: 5 July 2018 / Accepted: 11 July 2018 / Published: 13 July 2018
(This article belongs to the Special Issue Laser-Based Nano Fabrication and Nano Lithography)
The technique of laser ablation in liquids (LAL) has already demonstrated its flexibility and capability for the synthesis of a large variety of surfactant-free nanomaterials with a high purity. However, high purity can cause trouble for nanomaterial synthesis, because active high-purity particles can spontaneously grow into different nanocrystals, which makes it difficult to accurately tailor the size and shape of the synthesized nanomaterials. Therefore, a series of questions arise with regards to whether particle growth occurs during colloid storage, how large the particle size increases to, and into which shape the particles evolve. To obtain answers to these questions, here, Ag particles that are synthesized by femtosecond (fs) laser ablation of Ag in acetone are used as precursors to witness the spontaneous growth behavior of the LAL-generated surfactant-free Ag dots (2–10 nm) into different polygonal particles (5–50 nm), and the spontaneous size separation phenomenon by the carbon-encapsulation induced precipitation of large particles, after six months of colloid storage. The colloids obtained by LAL at a higher power (600 mW) possess a greater ability and higher efficiency to yield colloids with sizes of <40 nm than the colloids obtained at lower power (300 mW), because of the generation of a larger amount of carbon ‘captors’ by the decomposition of acetone and the stronger particle fragmentation. Both the size increase and the shape alteration lead to a redshift of the surface plasmon resonance (SPR) band of the Ag colloid from 404 nm to 414 nm, after storage. The Fourier transform infrared spectroscopy (FTIR) analysis shows that the Ag particles are conjugated with COO– and OH– groups, both of which may lead to the growth of polygonal particles. The CO and CO2 molecules are adsorbed on the particle surfaces to form Ag(CO)x and Ag(CO2)x complexes. Complementary nanosecond LAL experiments confirmed that the particle growth was inherent to LAL in acetone, and independent of pulse duration, although some differences in the final particle sizes were observed. The nanosecond-LAL yields monomodal colloids, whereas the size-separated, initially bimodal colloids from the fs-LAL provide a higher fraction of very small particles that are <5 nm. The spontaneous growth of the LAL-generated metallic particles presented in this work should arouse the special attention of academia, especially regarding the detailed discussion on how long the colloids can be preserved for particle characterization and applications, without causing a mismatch between the colloid properties and their performance. The spontaneous size separation phenomenon may help researchers to realize a more reproducible synthesis for small metallic colloids, without concern for the generation of large particles. View Full-Text
Keywords: laser ablation in liquids; particle growth; carbon encapsulation; polygonal particle; core-shell particle; surfactant-free laser ablation in liquids; particle growth; carbon encapsulation; polygonal particle; core-shell particle; surfactant-free
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MDPI and ACS Style

Zhang, D.; Choi, W.; Jakobi, J.; Kalus, M.-R.; Barcikowski, S.; Cho, S.-H.; Sugioka, K. Spontaneous Shape Alteration and Size Separation of Surfactant-Free Silver Particles Synthesized by Laser Ablation in Acetone during Long-Period Storage. Nanomaterials 2018, 8, 529. https://doi.org/10.3390/nano8070529

AMA Style

Zhang D, Choi W, Jakobi J, Kalus M-R, Barcikowski S, Cho S-H, Sugioka K. Spontaneous Shape Alteration and Size Separation of Surfactant-Free Silver Particles Synthesized by Laser Ablation in Acetone during Long-Period Storage. Nanomaterials. 2018; 8(7):529. https://doi.org/10.3390/nano8070529

Chicago/Turabian Style

Zhang, Dongshi, Wonsuk Choi, Jurij Jakobi, Mark-Robert Kalus, Stephan Barcikowski, Sung-Hak Cho, and Koji Sugioka. 2018. "Spontaneous Shape Alteration and Size Separation of Surfactant-Free Silver Particles Synthesized by Laser Ablation in Acetone during Long-Period Storage" Nanomaterials 8, no. 7: 529. https://doi.org/10.3390/nano8070529

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