Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

Gold nanorods have been receiving extensive attention owing to their extremely attractive applications in biomedical technologies, plasmon-enhanced spectroscopies, and optical and optoelectronic devices. The growth methods and plasmonic properties of Au nanorods have therefore been intensively studied. In this review, we present a comprehensive overview of the flourishing field of Au nanorods in the past five years. We will focus mainly on the approaches for the growth, shape and size tuning, functionalization, and assembly of Au nanorods, as well as the methods for the preparation of their hybrid structures. The plasmonic properties and the associated applications of Au nanorods will also be discussed in detail.

Gold nanorods and their plasmonic properties

The unique characteristics of ultrafast lasers, such as picosecond and femtosecond lasers, have opened up new avenues in materials processing that employ ultrashort pulse widths and extremely high peak intensities. Thus, ultrafast lasers are currently used widely for both fundamental research and practical applications. This review describes the characteristics of ultrafast laser processing and the recent advancements and applications of both surface and volume processing. Surface processing includes micromachining, micro- and nanostructuring, and nanoablation, while volume processing includes two-photon polymerization and three-dimensional (3D) processing within transparent materials. Commercial and industrial applications of ultrafast laser processing are also introduced, and a summary of the technology with future outlooks are also given. Scientists in Asia have reviewed the role of ultrafast lasers in materials processing. Koji Sugioka from RIKEN in Japan and Ya Cheng from the Shanghai Institute of Optics and Fine Mechanics in China describe how femtosecond and picosecond lasers can be used to perform useful tasks in both surface and volume processing. Such lasers can cut, drill and ablate a variety of materials with high precision, including metals, semiconductors, ceramics and glasses. They can also polymerize organic materials that contain a suitable photosensitizer and can three-dimensionally process inside transparent materials such as glass, and are already being used to fabricate medical stents, repair photomasks, drill ink-jet nozzles and pattern solar cells. The researchers also explain the characteristics of such lasers and the interaction of ultrashort, intense pulses of light with matter.

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Ultrafast lasers—reliable tools for advanced materials processing

The ground-state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero-point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si-C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC-MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.201605504

Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field

The rapid development of the femtosecond laser has revolutionized materials processing due to its unique characteristics of ultrashort pulse width and extremely high peak intensity. The short pulse width suppresses the formation of a heat-affected zone, which is vital for ultrahigh precision fabrication, whereas the high peak intensity allows nonlinear interactions such as multiphoton absorption and tunneling ionization to be induced in transparent materials, which provides versatility in terms of the materials that can be processed. More interestingly, irradiation with tightly focused femtosecond laser pulses inside transparent materials makes three-dimensional (3D) micro- and nanofabrication available due to efficient confinement of the nonlinear interactions within the focal volume. Additive manufacturing (stereolithography) based on multiphoton absorption (two-photon polymerization) enables the fabrication of 3D polymer micro- and nanostructures for photonic devices, micro- and nanomachines, and microfluidic devices, and has applications for biomedical and tissue engineering. Subtractive manufacturing based on internal modification and fabrication can realize the direct fabrication of 3D microfluidics, micromechanics, microelectronics, and photonic microcomponents in glass. These microcomponents can be easily integrated in a single glass microchip by a simple procedure using a femtosecond laser to realize more functional microdevices, such as optofluidics and integrated photonic microdevices. The highly localized multiphoton absorption of a tightly focused femtosecond laser in glass can also induce strong absorption only at the interface of two closely stacked glass substrates. Consequently, glass bonding can be performed based on fusion welding with femtosecond laser irradiation, which provides the potential for applications in electronics, optics, microelectromechanical systems, medical devices, microfluidic devices, and small satellites. This review paper describes the concepts and principles of femtosecond laser 3D micro- and nanofabrication and presents a comprehensive review on the state-of-the-art, applications, and the future prospects of this technology.

Femtosecond laser three-dimensional micro- and nanofabrication

The interactions often appear as two oppositecases, namely weak and strong couplings. In the weakcoupling regime, wavefunctions of molecules and SP modesof plasmons are considered to be unperturbed. The strongcoupling or coherent coupling occurs when resonant exciton–plasmon interactionsmodifymolecularwavefunctions andSPmodes, whereby the excitation energy is shared and oscillatesbetween the plasmonic and molecular systems (Rabi oscil-lations), leading to vacuum Rabi splitting of energy levels atthe resonance frequency. This is similar to behaviors ofpolaritons in an optical microcavity.

Hybrid-state dynamics of gold nanorods/dye J-aggregates under strong coupling.

Dammann gratings, as beam splitters and coherent signal generators, were produced in a short fabricating cycle by femtosecond laser fabrication via two-photon photopolymerization. These holograms that each generated 2×2, 3×3, 4×4, 5×5, and 6×6 spot sources in the fan-out demonstrated diffraction efficiency of 36%, 25%, 29%, 52%, and 49%, respectively, comparable with the theoretical values. This work shows the promising prospect of femtosecond laser fabrication in compatibly manufacturing various micro-optical devices including Dammann gratings and their integrated systems.

Dammann gratings as integratable micro-optical elements created by laser micronanofabrication via two-photon photopolymerization.

Although unique properties such as creation of nondiffracting beams and as a result the large focal depth have been exhibited from axicon lenses, and numerous important applications in optical signal processing and imaging have been demonstrated, axicons of dimensions smaller than a hundred of micrometers have not yet been reported. It is technically quite challenging for the currently available technologies including lithography and mechanical shaping to define complicated three-dimensional surface profiles depicted by lens functions in the small scale. Here, we report the solution of the issue by use of femtosecond laser nanofabrication via two-photon polymerization of resins. Not only well-defined monolithic micro axicons are attained, they demonstrate excellent optical characteristics: the cross-sectional Besselian beam intensity distribution was found almost unchanged for at least 200 ?m within the focal range; imaging remains unblurred and in high contrast in a much wider range than that for a common lens. The direct laser nanowriting strategy would allow the lens integrated with other optical components produced the same way, or incorporated to an existing micro-optical system.

Wen-Quan Wang

Papers

Hybrid-state dynamics of gold nanorods/dye J-aggregates under strong coupling.

Dammann gratings as integratable micro-optical elements created by laser micronanofabrication via two-photon photopolymerization.

Mask-Free Production of Integratable Monolithic Micro Logarithmic Axicon Lenses