3D Metallic Nanostructure Fabrication by Surfactant‐Assisted Multiphoton‐Induced Reduction

Cao, Yonghao; Takeyasu, Nobuyuki; Tanaka, Takuo; Duan, Xuan Ming; Kawata, Satoshi

doi:10.1002/smll.200801179

Cited by 225 publications

(216 citation statements)

References 28 publications

(30 reference statements)

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“…Many micro/nano fabrication techniques featuring 3D structures that could be applied to photonic and MMs have been developed in recent years. These techniques include layer-by-layer stacking 3,14,15 , structural rolling 16,17 , shadow evaporation 18 , multilayer electroplating 19 , membrane projection lithography 20,21 , stress-driven assembly 22 , direct laser writing 8,[23][24][25][26][27][28] , and ion-beam irradiation [29][30][31] . However, effective fabrication of nanoscale 3D plasmonic structures that can be spatially oriented with a hierarchical geometry remains challenging.…”

Section: Introductionmentioning

confidence: 99%

Directly patterned substrate-free plasmonic “nanograter” structures with unusual Fano resonances

et al. 2015

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The application of three-dimensional (3D) plasmonic nanostructures as metamaterials (MMs), nano-antennas, and other devices faces challenges in producing metallic nanostructures with easily definable orientations, sophisticated shapes, and smooth surfaces that are operational in the optical regime and beyond. Here, we demonstrate that complex 3D nanostructures can be readily achieved with focused-ion-beam irradiation-induced folding and examine the optical characteristics of plasmonic ''nanograter'' structures that are composed of free-standing Au films. These 3D nanostructures exhibit interesting 3D hybridization in current flows and exhibit unusual and well-scalable Fano resonances at wavelengths ranging from 1.6 to 6.4 mm. Upon the introduction of liquids of various refractive indices to the structures, a strong dependence of the Fano resonance is observed, with spectral sensitivities of 1400 nm and 2040 nm per refractive index unit under figures of merit of 35.0 and 12.5, respectively, for low-order and high-order resonance in the near-infrared region. This work indicates the exciting, increasing relevance of similarly constructed 3D free-standing nanostructures in the research and development of photonics and MMs.

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Section: Introductionmentioning

confidence: 99%

Directly patterned substrate-free plasmonic “nanograter” structures with unusual Fano resonances

et al. 2015

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“…[14][15][16] The method described here yields submicrometer silver structures that do not need to be self-supported because they are embedded inside a matrix. A doped polymer matrix is prepared using a mixture of silver nitrate (AgNO 3 ), polyvinylpyrrolidone (PVP) and water (H 2 O).…”

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confidence: 99%

A Method to Fabricate Disconnected Silver Nanostructures in 3D

Vora

Kang

Mazur

2012

JoVE

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The standard nanofabrication toolkit includes techniques primarily aimed at creating 2D patterns in dielectric media. Creating metal patterns on a submicron scale requires a combination of nanofabrication tools and several material processing steps. For example, steps to create planar metal structures using ultraviolet photolithography and electron-beam lithography can include sample exposure, sample development, metal deposition, and metal liftoff. To create 3D metal structures, the sequence is repeated multiple times. The complexity and difficulty of stacking and aligning multiple layers limits practical implementations of 3D metal structuring using standard nanofabrication tools. Femtosecond-laser direct-writing has emerged as a pre-eminent technique for 3D nanofabrication. 1,2 Femtosecond lasers are frequently used to create 3D patterns in polymers and glasses. [3][4][5][6][7] However, 3D metal direct-writing remains a challenge. Here, we describe a method to fabricate silver nanostructures embedded inside a polymer matrix using a femtosecond laser centered at 800 nm. The method enables the fabrication of patterns not feasible using other techniques, such as 3D arrays of disconnected silver voxels. 8 Disconnected 3D metal patterns are useful for metamaterials where unit cells are not in contact with each other, 9 such as coupled metal dot 10,11 or coupled metal rod 12,13 resonators. Potential applications include negative index metamaterials, invisibility cloaks, and perfect lenses.In femtosecond-laser direct-writing, the laser wavelength is chosen such that photons are not linearly absorbed in the target medium. When the laser pulse duration is compressed to the femtosecond time scale and the radiation is tightly focused inside the target, the extremely high intensity induces nonlinear absorption. Multiple photons are absorbed simultaneously to cause electronic transitions that lead to material modification within the focused region. Using this approach, one can form structures in the bulk of a material rather than on its surface.Most work on 3D direct metal writing has focused on creating self-supported metal structures. 14-16 The method described here yields submicrometer silver structures that do not need to be self-supported because they are embedded inside a matrix. A doped polymer matrix is prepared using a mixture of silver nitrate (AgNO 3 ), polyvinylpyrrolidone (PVP) and water (H 2 O). Samples are then patterned by irradiation with an 11-MHz femtosecond laser producing 50-fs pulses. During irradiation, photoreduction of silver ions is induced through nonlinear absorption, creating an aggregate of silver nanoparticles in the focal region. Using this approach we create silver patterns embedded in a doped PVP matrix. Adding 3D translation of the sample extends the patterning to three dimensions. Video LinkThe video component of this article can be found at

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“…High resolution SEMs (Figure 2) show that the metallic patterns are comprised of small metallic granules, indicating that the rate of photoreduction within the focal volume is limited by the diffusion of metallic precursors. [32][33][34] SEM cross-sectional analysis of an exemplary Pd structure revealed that the granular surface, in large part, is continuous throughout the structure interior down to the glass/metal interface at which point the structure appears solidified, indicating thermal melting/annealing at the interface-a consequence of heating via light absorption by the metallic pads. We estimated the steady state temperature rise (ΔΤ) at the laser focal point of the glass/metal interface using the solution for the low frequency limit (essentially CW) of the laser modulation: 35…”

Section: Supporting Information Placeholdermentioning

confidence: 99%

Multiphoton Lithography of Nanocrystalline Platinum and Palladium for Site-Specific Catalysis in 3D Microenvironments

et al. 2012

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Integration of catalytic nanostructured platinum and palladium within 3D microscale structures or fluidic environments is important for systems ranging from micropumps to microfluidic chemical reactors and energy converters. We report a straightforward procedure to fabricate microscale patterns of nanocrystalline platinum and palladium using multiphoton lithography. These materials display excellent catalytic, electrical, and electrochemical properties, and we demonstrate high-resolution integration of catalysts within 3D defined microenvironments to generate directed autonomous particle and fluid transport.

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3D Metallic Nanostructure Fabrication by Surfactant‐Assisted Multiphoton‐Induced Reduction

Cited by 225 publications

References 28 publications

Directly patterned substrate-free plasmonic “nanograter” structures with unusual Fano resonances

Directly patterned substrate-free plasmonic “nanograter” structures with unusual Fano resonances

A Method to Fabricate Disconnected Silver Nanostructures in 3D

Multiphoton Lithography of Nanocrystalline Platinum and Palladium for Site-Specific Catalysis in 3D Microenvironments

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