Over the last two decades, considerable progress has been made in the field of two-photon polymerization lithography (TPL) [1-5], which has resulted in a wide range of applications in biotechnology, microfluidics, microrobotics, photonics and antiforgery. Exploiting the nonlinear dependency of the polymerization rate on light intensity, TPL is suited best to produce true three-dimensional structures with feature sizes beyond the diffraction limit [2]. Nevertheless, most of the materials and techniques employed for 3D manufacturing are limited to the fabrication of objects with uniform and/or static material's properties. One of the current challenges of TPL is to impart the objects with further functionalities (often called "4D printing"), such as the ability to dynamically respond to external stimuli (i.e. temperature, light, pH, humidity, etc.) [3, 4] or to spatially modulate their properties (i.e., optical, mechanical, etc.) at the microscale [5-7]. Here we report a simple feasible strategy to provide the "color dimension" to 3D microobjects, adopting a dye-free structural color printing. We take advantage of the self- organized supramolecular helical structure of a photonic photoresist, namely cholesteric reactive mesogens (CRMs), and of the "gray-tone" TPL approach [3], which allows for fine tuning the intrinsic photonic band gap (PBG) of the CRMs, at the microscale, during the fabrication by adjusting the laser exposure dose [7]. Altering the crosslinking density of the CRMs polymer network, the shrinkage of polymer is exploited to control the effective helix pitch, still guaranteeing compact solid structures. Thus, full color mapping across the whole visible range is demonstrated in a rapid, single-step TPL fabrication session. In view of the potential application impact in the fields of miniaturized optics, lasers, and anti-counterfeiting, a 4D quick response (QR) code, made of 25 × 25 micron- sized square cuboid elements with different heights and selective reflection color bands, is reported as a novel paradigm of secure authentication code. References [1] S. Kawata, et al. "Finer features for functional microdevices" Nature, 412, 697, 2001 [2] V. Harinarayana, Y.C. Shin, "Two-photon lithography for three-dimensional fabrication in micro/nanoscale regime: A comprehensive review" Optics & Laser Technology, 142, 107180, 2021 [3] C. A. Spiegel, et al. "4D printing at the microscale" Adv. Funct. Mater. 30, 1907615, 2020 [4] M. del Pozo, et al. "Direct laser writing of four-dimensional structural color microactuators using a photonic photoresist" ACS Nano 14, 9832, 2020 [5] Y. Liu, et al. "Structural color three-dimensional printing by shrinking photonic crystals" Nat. Comm. 10, 4340, 2019 [6] S. Nocentini, et al. "Structured optical materials controlled by light" Adv. Optical Mater. 6, 1800167, 2018 [7] T. Ritacco, et al. "Tuning cholesteric selective reflection in situ upon two-photon polymerization enables structural multicolor 4D microfabrication" Adv. Optical Mater. 10, 2101526, 2022
Full-color 4D two-photon lithography made easy
A Mazzulla;M Giocondo;P Pagliusi
2022
Abstract
Over the last two decades, considerable progress has been made in the field of two-photon polymerization lithography (TPL) [1-5], which has resulted in a wide range of applications in biotechnology, microfluidics, microrobotics, photonics and antiforgery. Exploiting the nonlinear dependency of the polymerization rate on light intensity, TPL is suited best to produce true three-dimensional structures with feature sizes beyond the diffraction limit [2]. Nevertheless, most of the materials and techniques employed for 3D manufacturing are limited to the fabrication of objects with uniform and/or static material's properties. One of the current challenges of TPL is to impart the objects with further functionalities (often called "4D printing"), such as the ability to dynamically respond to external stimuli (i.e. temperature, light, pH, humidity, etc.) [3, 4] or to spatially modulate their properties (i.e., optical, mechanical, etc.) at the microscale [5-7]. Here we report a simple feasible strategy to provide the "color dimension" to 3D microobjects, adopting a dye-free structural color printing. We take advantage of the self- organized supramolecular helical structure of a photonic photoresist, namely cholesteric reactive mesogens (CRMs), and of the "gray-tone" TPL approach [3], which allows for fine tuning the intrinsic photonic band gap (PBG) of the CRMs, at the microscale, during the fabrication by adjusting the laser exposure dose [7]. Altering the crosslinking density of the CRMs polymer network, the shrinkage of polymer is exploited to control the effective helix pitch, still guaranteeing compact solid structures. Thus, full color mapping across the whole visible range is demonstrated in a rapid, single-step TPL fabrication session. In view of the potential application impact in the fields of miniaturized optics, lasers, and anti-counterfeiting, a 4D quick response (QR) code, made of 25 × 25 micron- sized square cuboid elements with different heights and selective reflection color bands, is reported as a novel paradigm of secure authentication code. References [1] S. Kawata, et al. "Finer features for functional microdevices" Nature, 412, 697, 2001 [2] V. Harinarayana, Y.C. Shin, "Two-photon lithography for three-dimensional fabrication in micro/nanoscale regime: A comprehensive review" Optics & Laser Technology, 142, 107180, 2021 [3] C. A. Spiegel, et al. "4D printing at the microscale" Adv. Funct. Mater. 30, 1907615, 2020 [4] M. del Pozo, et al. "Direct laser writing of four-dimensional structural color microactuators using a photonic photoresist" ACS Nano 14, 9832, 2020 [5] Y. Liu, et al. "Structural color three-dimensional printing by shrinking photonic crystals" Nat. Comm. 10, 4340, 2019 [6] S. Nocentini, et al. "Structured optical materials controlled by light" Adv. Optical Mater. 6, 1800167, 2018 [7] T. Ritacco, et al. "Tuning cholesteric selective reflection in situ upon two-photon polymerization enables structural multicolor 4D microfabrication" Adv. Optical Mater. 10, 2101526, 2022I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
