A pilot study on laser 3D printing of inorganic free-form micro-optics is experimentally validated. Ultrafast laser nanolithography is employed for structuring hybrid organic-inorganic material SZ2080^TM followed by high-temperature calcination post-processing. The combination allows production of 3D architectures and the heat-treatment results in converting the material to inorganic substance. The produced miniature optical elements are characterized and their optical performance is demonstrated, focusing and imaging properties are evaluated. Finally, the concept is validated for manufacturing compound optical components such as stacked lenses. This is opening for new directions and applications of laser made microoptics under harsh conditions such as radiation, temperature, acidic environment, pressure variations, which include open space, astrophotonics, and remote sensing.
Here we report on the laser manufacturing of glass true 3D micro-optics. We demonstrate the feasibility of producing individual free-form geometry elements such as lenses, prisms, gratings proving the potential of integration into monolith stacked components. This is achieved by combining ultrafast laser 3D nanolithography and subsequent thermal post-treatment (calcination) - a novel approach introduced for additive manufacturing of inorganic materials [Nanoscale Horiz. 4, 647 (2019)]). The laser made pristine micro-optical components maintain their predefined shape while material is converted from hybrid polymer to glass corresponding to its inherent refractive index and transparency. This approach enables both realization of complex geometries and variation of material properties simultaneously.
Ceramics play an important role in today’s science and industry as it can withstand immense thermal, mechanical, chemical and other hazards. In recent years, the interest in 3D printing micro- or even nano-structures out of ceramics has been growing rapidly. Therefore, direct laser writing by two photon polymerization together with calcination have been proved to be a powerful tool for the fabrication of fully 3D glass-ceramic objects in micro- and nano-scale [1]. However, producing such structures with unique properties at meso scale (features from nm to cm overall size) is one of the greatest challenges [2]. In order to overcome it the composition of the starting materials and as well as conditions of calcination have to be fully understood and enhanced.
We synthesized a series of organic-inorganic polymer precursors via sol-gel method varying the molar ratio of silicon (Si) and zirconium (Zr) complexes (Si:Zr, where Si=9; 8; 7; 6; 5 and Zr=1; 2; 3; 4; 5) [3] and investigated 3D processing of these materials. The study shows that the “glassy” phase structures retain their shape without any distortion. Furthermore, calcination provides a route for the continuous size control and formation of a variety of phase transformation for free-form nano-/micro-objects. It is shown that due to the isotropic nature of the shrinkage during calcination fabricated 3D objects retain complex geometry. Nano-woodpiles, bulk-woodpile hybrids and full bulk structures are formed. The sizes of single features in these objects vary from 120 nm to 800 nm with overall size going to 30 µm. Finally, changes in focused ion beam machining rates between standard and calcinated materials are shown proving enhanced resiliency of the final product (up to 50%).
[1] Gailevičius, D., et al., Additive-manufacturing of 3D glass-ceramics down to nanoscale resolution. Nanoscale Horiz.;
4, 647-651; (2019)
[2] L. Jonusauskas, D. Gailevicius, S. Rekstyte, T. Baldacchini, S. Juodkazis, M. Malinauskas, Mesoscale Laser 3D Printing, Opt. Express
27 (11), 15205-15221 (2019)
[3] Ovsianikov, A., et al., Ultra-Low Shrinkage Hybrid Photosensitive Material for Two-Photon Polymerization Microfabrication. ACS Nano; 2(11), 2257-2262; (2008)
Even though graphene is a gapless material, it demonstrates strong interband absorption from a broad range of wavelengths between VIS and NIR. Recent photocurrent graphene-based detectors demonstrated strong photoresponse signal near the graphene/metal boundaries. To increase the response time of photodetectors, the use of low thermal capacity materials and structures are required. SiN membranes are good candidates due to their high-quality factor (up to 106-107), low mass and excellent optical properties. The motivation for this study was based on a lack of any suitable solution for nano-dimension form factor detector that could be integrated into 3D photonic bandgap structures for real-time internal characterization.
Ultrafast laser lithography allows additive fabrication of 3D sub-micrometric size objects in various materials. Here we demonstrate significant new capabilities achievable with this approach by using hybrid organic–inorganic material as the initial medium for laser structuring, and adding a high-temperature post-fabrication treatment. Calcination at temperatures of up to 1500°C leads to decomposition of the organic component in the initial material, and sintering of the inorganic component into a stable matrix. This results in the final object composed purely of glass-ceramic material, and having volume and size significantly reduced in comparison to those of the initial object. Possibilities to control both the composition and degree of the thermal down-scaling will be demonstrated. The proposed new pathway to inorganic 3D nanoscale objects and structures is easy to implement, and allows one to significantly surpass the spatial resolution and feature size achievable using laser lithography only. We study optical properties of transparent inorganic microstructures and optimize them for specific photonic functions. In the future it may be useful in space and defense-related areas for realization of chemically and thermally resilient photonic components, such as narrow-band IR emitters and optical sensors to be used in nuclear power plants and other harsh environments.
Reference
D. Gailevicius, V. Padolskyte, L. Mikoliunaite, S. Sakirzanovas, S. Juodkazis, and M. Malinauskas, ”Additive-Manufacturing of 3D Glass-Ceramics down to Nanoscale Resolution,” Nanoscale Horiz., 10.1039/C8NH00293B (2019), online first.
In this work we reveal an influence of polarization of the laser beam on polymerization in direct laser writing. It was experimentally found that the width of suspended lines fabricated in SZ2080, OrmoComp and PETA (pentaerythritol triacrylate) pre-polymers directly depends on the incident polarization and is largest when the angle between the electric field vector and the sample translation direction is α = 90° and the smallest when α = 0°. The size of polymerized structures is consistent with theoretical simulations based on vectorial Debye theory. Experiments were performed by using average laser power corresponding to the middle value of the fabrication window. Polarization was found to be affecting feature sizes while structuring various widespread photoresists, the observed variation was material dependent and measured from 5 to 22% in the line-width. The performed study proves that polarization can be used as a variable parameter for fine tuning of the voxel's aspect ratio.
KEYWORDS: Temperature metrology, Laser processing, 3D metrology, Multiphoton lithography, Polymerization, Scanning electron microscopy, 3D microstructuring, Nanolithography, In situ metrology, Laser damage threshold
Luminescence measurements of upconverting nanocrystals (UCNCs) dispersed in SZ2080 hybrid prepolymer being processed under different laser polymerization regimes are presented. Er3+ ions doped β-NaYbF4 UCNCs were prepared by a one-step thermal decomposition method. The ratio of the 2H11/2 → 4I15/2 and 4S3/2→ 4I15/2 emission intensities under λ= 980 nm excitation in the range from 24 to 70°C confirmed to follow Boltzmann type distribution and enabled a self-referenced optical readout of the sample temperature changes. Variation of thermally-coupled spectral bands intensity ratio was observed under typical laser writing conditions (1030 nm, 300 fs, 200 kHz, NA = 0.8) and E(pulse) varying from below threshold to the optical breakdown. Average fitted temperature changes around polymerized voxel calculated to be ΔT1<3 K within polymerization window and increases up to ΔT2 ≈ 170 K in overexposing regime.
Nano-texturing of surface by self-organised ablation ripples as well as modifications of internal volume of materials, transparent at the wavelength of laser irradiation, is gaining interest due to simplicity of direct laser writing/printing. With ultra-short laser pulses (τp < 1 ps) a wider range of structuring morphologies is accessible, namely, sub-wavelength ripples. The surface wave formed on the plasma-dielectric (air or substrate) explains difference of the formed pattern. These corresponding front- and back-side (in respect to the incoming laser beam) modes of laser structuring accounts for the ripple formation inside transparent materials, where a skin-layer plasma is formed. Emerging applications of nano-textured surfaces for bio-medical field are discussed.
Luminescence measurements of upconverting nanocrystals (UCNCs) dispersed in SZ2080 prepolymer being pro- cessed by direct laser writing (DLW) nanopolymerization technique are presented. Er3+ ions doped β-NaYbF4 and Er3+,Yb3+ co-doped β-NaGdF4 core and core-shell UCNCs were prepared by a thermal decomposition method. The ratio of the 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 emission intensities under λ = 975 nm excitation was confirmed to follow Boltzmann-type distribution in the temperature range from 20 °C to 200 °C and enabled a self-referenced optical readout of the sample temperature changes. Variation of thermally-coupled spectral bands fluorescence intensity ratio (FIR) was observed while prepolymer being processed under typical DLW conditions (1030 nm, 300 fs, 200 kHz, NA = 0.8) and Epulse varying from below modification threshold to the optical breakdown. Average fitted temperature changes around polymerized voxel measured ∆T1 < 30 °C within polymerization window and increases up to ∆T2~100 °C in overexposing regime.
Three dimensional (3D) fast (< 0.5 hour) printing of micro-optical elements down to sub-wavelength resolution over 100 μm footprint areas using femtosecond (fs-)laser oscillator is presented. Using sub-1 nJ pulse energies, optical vortex generators made of polymerised grating segments with an azimuthally changing orientation have been fabricated in SZ2080 resist; width of polymerised rods was ~ 150 nm and period 0.6-1 μm. Detailed phase retardance analysis was carried out manually with Berek compensator (under a white light illumination) and using an equivalent principle by an automated Abrio implementation at 546 nm. Direct experimental measurements of retardance was required since the period of the grating was comparable (or larger) than the wavelength of visible light. By gold sputtering, transmissive optical vortex generators were turned into reflective ones with augmented retardance, Δn × h defined by the form birefringence, Δn, and the height h = 2d where d is the thickness of the polymerised structure. Retardance reached 315 nm as measured with Berek compensator at visible wavelengths. Birefringent phase delays of π (or λ/2 in wavelength) required for high purity vortex generators can be made based on the proposed approach. Optical vortex generators for telecom wavelengths with sub-wavelength patterns of azimuthally oriented gratings are amenable by direct laser polymerisation.
Mixing of lithographically processable materials with functional additives is one of the widely explored possibilities in the field of the laser material processing. In this work we investigate how gold nanoparticles (Au NP) influence the photosensitivity of SZ2080 and PEG-DA-700 – two materials commonly used in femtosecond 3D direct laser writing (DLW). Experimental study of achieved line widths as well as comparison of polymerization/optical damage threshold intensities allowed quantitatively define how Au NP change polymers’ response to ultrafast laser pulses. Light-material and plasmonic interaction theories are applied to explain this phenomena. Furthermore, we demonstrate how nanoprecision achieved with DLW can be employed to create functional micromechanical structures, namely negative Poisson coefficient metamaterial and chain-mail like flexible structure. Later one is produced using combination of linear stages and galvanoscanners, demonstrating nearly unlimited working area (in range of ∼cm) and very high translation velocity (∼mm/s) thus proving that DLW can be considered an industrial grade technology.
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