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Abstract: With the development of nanotechnology, emerging nanotechniques compel dramatically increasing demands on fabrication technique for realizing nanostructures. As an important approach, direct laser writing has demonstrated extraordinary capabilities in fabricating three-dimensional (3D) micro/nanostructure, which stems from spatially resolved focal spot by tightly focusing laser beams. The unique 3D feature fabrication allows volumetrically integrating multiple electro- or opto-functionalities in micro/nanodevices, and thus, is promising for advancing various modern scientific technological fields such as next generation of micromechanics and opto-nanodevices. However, the feature size of structures as fabricated as well as resolution in fabrication is subject to a fundamental limit set by the diffraction nature of light. In this regard, the minimum feature size of structures as fabricated is commonly constrained from half the wavelength of the light output by the laser source. To improve resolution beyond the optical diffraction limit, in this review, we introduce a dual-beam super-resolution direct laser writing technique. Combined with two-photon polymerization (TPP) method and stimulated emission depletion (STED) principle, the technique has successfully realized resolution much finer than its counterpart being obtained based on Abbe’s law, and uphold exceptional 3D nanofabrication scheme. The principle of dual-beam super-resolution laser direct writing and recent progress in improving line width and resolution have been demonstrated in the review. In general, two beams are employed in the fabrication. One beam, so called initiating beam, is used to initiate optical reactions such as photo-polymerization, and the other, namely the inhibiting beam, is used to inhibit the optical reaction. While the initiating beam is modulated to Gaussian shape, the inhibiting beam can be shaped into Laguerre-Gaussian mode with zero light intensity in the center. By overlapping these two beams in the focal region, the inhibiting can inhibit the fabrication in its out ring, leaving the center of the initiating beam in function. As a result, a super-resolved focal spot can be obtained with tuning the intensity ratio of the two beams. To further improve resolution to nanoscale, delicate design to the photoresin material and the focal field is required. For instance, optimizing the inhibition efficiency upon the exposure to the inhibiting beam enables 9 nm free-standing line equivalent to one eighty-ninth of the wavelength of the initiating beam. Moreover, we have also summarized emerging applications of dual-beam super-resolution laser direct writing in relevant fields, such as opto-devices with photonic band gap in visible region and biology. Eventually, challenges in how to fulfill low-cost, high efficiency, large area and multi-functional materials’ fabrication and its future development are discussed.
Schematic diagram of dual-beam super-resolution fabrication.
Simulations of phase modulation point spread functions of laser focus. (a) Without phase-plate. (b) With 2π spiral phase-plate. (c) With annular phase-plate.
Schematic diagram of the molecular states and transitions for different depletion mechanisms based on photo-initiating and photo-inhibiting principle. (a) Photo-induced chain radical inhibition (PCI). Photoinitiator molecules are excited and generate radicals(R•) which lead to monomer photopolymerization, photoinhibitor molecules are excited and generate radicals(Q•) to clear radicals(R•), thus to terminate propagating polymer chains(RM•). (b) Photo-induced stimulated emission inhibition(PSI). Photoinitiator molecules are excited to active excitation station by two-photon absorption, via intersystem crossing reaching to triplet state, and generate radicals(R•) leading to photopolymerization, the inhibition beam deactivates photointiator molecules by stimulated emission, thus to inhibit radicals' generation and propagating polymer chains(RM•). (c) Photo-induced intermediate state inhibition(PMI). Photoinitiator molecules are excited by two-photon absorption to a long-lived intermediate state, with some active species generation, leading to photopolymerization. Under inhibition laser irrigation, the intermediate state is deactivated and inhibit the cross-linking polymerization[1, 13].
(a) SEM images of voxels created with inhibition beam powers of 0 mW, 17 mW, 34 mW, 50 mW, 84 mW and 100 mW (left to right, top to bottom). (b) Dependence of the height and aspect ratio of voxels on the power of the deactivation beam. (c) Three-dimensional tower with rings structure [22].
SEM of polymer voxels features with donut-shaped inhibition laser irradiation. The excitation power was held at 10 μW while the depletion power was progressively increased, from left to right, 0 μW, 1 μW, 2.5 μW, 10 μW and 100 μW. (b) Fitting curve of voxels fabricated with 10 μW of excitation power and 110 μW of depletion power. (c) Polymer column fabricated by using the same conditions as Fig. 5(b), at a velocity of 0.125 μm/s for 3 μm[21].
Polymer linewidth versus power of the continuous-wave 532 nm wavelength depletion beam. The power of the two-photon excitation beam centered around 810 nm wavelength is fixed to 13.5 mW. (a)~(f) Exhibit electron micrographs illustrating the raw data underlying the data points[23].
(a) Two-line resolution versus the intensity of the inhibition laser beam, line resolution gradually improved with depletion power increasing, reaching 52 nm in G dot. (b) Feature size of free-standing lines versus the intensity of the inhibition beam, feature size gradually decreased with depletion power increasing, reaching 9 nm in E dot[20].
(a) SEM images of MPOEA/PETA photoresist linewidth without depletion power and minimum linewidth with depletion power increasing, relationship between linewidth and depletion power increasing (right). (b) SEM images of CEA/PETA photoresist linewidth without depletion power and minimum linewidth with depletion power increasing, relationship between linewidth and depletion power increasing (right). (c) Confocal fluorescence images of the 3D composite multi-layer structure by dual-beam fabricating two different photoresists[28].
Schematic diagram of fabrication and processing of three-dimensional photonic bandgap crystals[31].
(a) Scanning electron micrographs of the polymer helices structures. (b) Scanning electron micrographs of the final gold helices structures. (c) Arrays of single helices fabricated on the same substrate and employing the same fabrication process. (d) Scanning electron micrograph of single helices as previously fabricated by conventional direct laser writing[32].
Demonstration of 3D parallelized recording through a volumetric superresolved multifocal array. (a) Scheme of 3D parallelized recording on the prefabricated multilayered structure with a layer separation of 1.5 μm. (b) SEM images of three layers of bit arrays recorded by superresolved multifocal array with a bit separation of 200 nm and uniform bit size of 80 nm[35].
(a) Nanoanchors fabricated by dual-beam super-resolution fabrication. Top: SEM image. Middle: auto fluorescence of the nanoanchors. Bottom: no auto fluorescence is detectable using 647 nm excitation. (b), (c) Under 647 nm excitation, fluorescence distribution of Atto655-labeled antibodies in nanoanchors array before washing and after washing. (d) Statistical distribution of fluorescence intensity counts per fluorescent spot during 5 ms collection time, obtained from: red sparsely and randomly distributed antibodies and blue from nanoanchors loaded with antibodies[36].
(a) Sketch of nanostructured dots (nanoanchors) incubated with fluorescent streptavidin. Only 10% of all dots were covered with proteins. (b) Sketch of fabricated dots having ~30% average streptavidin loading per dot. (c), (d) are sketches of the largest fabricated dots with over 80% and 100% streptavidin coverage[37].