Two-photon Polymerization Process Research Articles

Fabrication of hybrid Fabry-Pérot microcavity using two-photon lithography for single-photon sources.

For an efficient single-photon source a high-count rate into a well-defined spectral and spatial mode is desirable. Here we have developed a hybrid planar Fabry-Pérot microcavity by using a two-photon polymerization process (2PP) where coupling between single-photon sources (diamond colour centres) and resonance modes is observed. The first step consists of using the 2PP process to build a polymer table structure around previously characterized nitrogen-vacancy (NV) centres on top of a distributed Bragg reflector (DBR) with a high reflectivity at the NV zero-phonon line (ZPL). Afterwards, the polymer structure is covered with a silver layer to create a weak (low Q) cavity where resonance fluorescence measurements from the NVs are shown to be in good agreement with analytical and Finite Difference Time Domain (FDTD) results.

Scaffolds in a shell-a new approach combining one-photon and two-photon polymerization.

We report on a laser system combining one-photon and two-photon polymerization for precise and fast fabrication of macroscopic three-dimensional structures featuring microscale and nanoscale characteristics. This single-stage process significantly reduces the production time as demonstrated by scaffolds in a shell application. Porous scaffolds with different pore sizes are surrounded by a ring so that cells can be seeded directly to the scaffolds kept in a shell and do not spread over the whole substrate expecting a saving of cell suspension, faster growth on the scaffolds, and a more controllable environment. Compared to a two-photon polymerization process, the ring is fabricated about 500 times faster using one-photon polymerization. The presented hybrid process qualifies for further applications illustrated by a fluidic system.

Improvements in Resolution of Additive Manufacturing: Advances in Two-Photon Polymerization and Direct-Writing Electrospinning Techniques.

In recent years, additive manufacturing (AM) technologies have attracted significant interest in many industrial and research fields, particularly in tissue engineering. Printed structures used as physical and bioactive supports for tissue regeneration are becoming increasingly complex so as to mimic natural tissues in order to answer future medical needs. Reproducing the biological environment of a native tissue from the microscopic to the macroscopic scale appears to be the best strategy for effective regeneration. Recent advances in AM have led to the production of scaffolds designed with a high precision. This Review presents results concerning two AM technologies which enable the highest accuracy of scaffold design to be obtained, with a precision down to the nanoscale. The first technique is based on a two-photon polymerization (TPP) process, while the other is based on a direct-writing electrospinning (DWES) system. Here, we present an overview of the fabrication mechanisms, the final scaffold properties, and their applications in tissue engineering. The production of highly resolved structures offers new possibilities for studying cell behavior in a controlled environment and also for adjusting the desired scaffold properties to address current and future needs in tissue engineering. The current technical limitations and future challenges are thus also discussed in this Review.

Design and Fabrication of a Three-Dimensional Artificial Compound Eye Using Two-Photon Polymerization.

Microlens arrays have been widely used in the fields of micro-optics because of the advantages of their high diffraction efficiency, high fill factor, and wide operating band. However, the microlens array still has problems with its smaller field of view (FOV) and lower utilization of light energy. In this paper, a 3D compound eye system consisting of a microlens array and a pinhole array was designed according to the optical principle of insect compound eye. The artificial compound eye structure was processed in two-photon polymerization processing technology. Ray tracing and optical system simulation of the designed artificial compound eye structure were performed. The results showed that the artificial compound eye structure had a wider FOV and higher light energy utilization than a conventional 2D microlens array. This thesis may lay a theoretical foundation for the structural optimization design of microlens arrays.

Single-photon three-dimensional microfabrication through a multimode optical fiber.

Two-photon polymerization (TPP) processes have enabled the fabrication of advanced and functional microstructures. However, most TPP platforms are bulky and require the use of expensive femtosecond lasers. Here, we propose an inexpensive and compact alternative to TPP by adapting an endoscopic imaging system for single-photon three-dimensional microfabrication. The wavefront of a visible continuous-wave laser beam is shaped so that it focuses into a photoresist through a 5 cm long ultra-thin multimode optical fiber (∅70 μm, NA 0.64). Using this device, we show that single-photon polymerization can be confined to the phase-controlled focal spot thanks to the non-linearity of the photoresist, likely due to oxygen radical scavenging. Thus, by exploiting this non-linearity with a specific overcuring method we demonstrate single-photon three-dimensional fabrication of solid and hollow microstructures through a multimode fiber with a 1.0-μm lateral and 21.5-μm axial printing resolution. This opens up new possibilities for advanced and functional microfabrication through endoscopic probes with inexpensive laser sources.

3D computer-aided nanoprinting for solid-state nanopores.

Here we report on the generation of solid-state nanopores with controllable sizes and shapes based on direct laser writing with a computer-aided two-photon polymerization process. Through a theoretical and experimental study of the accumulation effect during the two-photon polymerization, we have achieved nanopores with an inner diameter of down to ∼λ/10 (76.9 nm) for the first time, which is far beyond Abbe's diffraction limit. The generated nanopores can be stacked to form a channel with desired asymmetric shapes. This work provides the potential to integrate the solid-state nanopores into functional devices and opens up a new avenue for optimizing the gating properties of artificial membranes.

Polarization-independent phase modulators enabled by two-photon polymerization

A double-layer polarization-independent liquid crystal (LC) phase modulator is demonstrated and characterized. Using two-photon polymerization process, an ultra-thin partition polymeric film to separate the LC cell into two layers with orthogonal alignment directions is fabricated. Such a thin partition film also helps to reduce the voltage shielding effect. Using a high birefringence and low viscosity LC mixture, 2π phase change at merely 10 V for a He-Ne laser beam is achieved, while keeping a fast response time. Simulation result agrees reasonably well with experimental data.

Laser polishing and 2PP structuring of inside microfluidic channels in fused silica

This study presents the development of post-processing steps for microfluidics fabricated with selective laser etching (SLE) in fused silica. In a first step, the SLE surface—even inner walls of microfluidic channels—can be smoothed by laser polishing. In addition, two-photon polymerization (2PP) can be used to manufacture polymer microstructures and microcomponents inside the microfluidic channels. The reduction in the surface roughness by laser polishing is a remelting process. While heating the glass surface above softening temperature, laser radiation relocates material thanks to the surface tension. With laser polishing, the RMS roughness of SLE surfaces can be reduced from 12 µm down to 3 nm for spatial wavelength λ < 400 µm. Thanks to the laser polishing, fluidic processes as well as particles in microchannels can be observed with microscopy. A manufactured microfluidic demonstrates that SLE and laser polishing can be combined successfully. By developing two-photon polymerization (2PP) processing in microchannels we aim to enable new applications with sophisticated 3D structures inside the microchannel. With 2PP, lenses with a diameter of 50 µm are processed with a form accuracy rms of 70 nm. In addition, this study demonstrates that 3D structures can be fabricated inside the microchannels manufactured with SLE. Thanks to the combination of SLE, laser polishing and 2PP, research is pioneering new applications for microfluidics made of fused silica.

Cross-Linkable Gelatins with Superior Mechanical Properties Through Carboxylic Acid Modification: Increasing the Two-Photon Polymerization Potential.

The present work reports on the development of photo-cross-linkable gelatins sufficiently versatile to overcome current biopolymer two-photon polymerization (2PP) processing limitations. To this end, both the primary amines as well as the carboxylic acids of gelatin type B were functionalized with photo-cross-linkable moieties (up to 1 mmol/g) resulting in superior and tunable mechanical properties (G′ from 5000 to 147000 Pa) enabling efficient 2PP processing. The materials were characterized in depth prior to and after photoinduced cross-linking using fully functionalized gelatin-methacrylamide (gel-MOD) as a benchmark to assess the effect of functionalization on the protein properties, cross-linking efficiency, and mechanical properties. In addition, preliminary experiments on hydrogel films indicated excellent in vitro biocompatibility (close to 100% viability) both in the presence of MC3T3 preosteoblasts and L929 fibroblasts. Moreover, 2PP processing of the novel derivative was superior in terms of applied laser power (≥40 vs ≥60 mW for gel-MOD at 100 mm/s) as well as post-production swelling (0–20% vs 75–100% for gel-MOD) compared to those of gel-MOD. The reported novel gelatin derivative (gel-MOD-AEMA) proves to be extremely suitable for direct laser writing as both superior mimicry of the applied computer-aided design (CAD) was obtained while maintaining the desired cellular interactivity of the biopolymer. It can be anticipated that the present work will also be applicable to alternative biopolymers mimicking the extracellular environment such as collagen, elastin, and glycosaminoglycans, thereby expanding current material-related processing limitations in the tissue engineering field.

Two-photon polymerization fabrication and Raman spectroscopy research of SU-8 photoresist using the femtosecond laser

In this work, a two-photon polymerization (2PP) processing device was built using the femtosecond laser, and femtosecond laser direct writing was performed on SU-8 photoresist. Due to the 2PP effect of the photoresist caused by the femtosecond laser, the polymeric line with size less than the focal spot size is obtained. Based on the Raman spectroscopy characterization of SU-8 polymer before and after 2PP, we research the dynamic process of femtosecond laser induced 2PP. In Raman spectra, some scattering peaks with large intensity variation, such as 1 108 cm-1 and 1 183 cm-1, indicate that the asymmetric stretching vibration of C-O-C bond in SU-8 polymer is increased. By comparison, we can find that 2PP only affects the light absorption of initiator, but does not affect the monomer polymerization. It is helpful to understand the interaction of photoresist and femtosecond laser, and plays an important role in quantitatively controlling the polymerization degree of SU-8 polymer and improving the processing resolution of 2PP.1

Photolithography of 3D Scaffolds for Artificial Tissue

The present study is focused on the design and fabrication of novel functional 3D-hydrogel scaffolds for regenerative medicine. In order to critically analyzing the effect of the microarchitecture of 3D scaffolds for driving the cellular fate and diffusion of progenitor stem cells we have fabricate a number of scaffolds with different geometry, stiffness and composition. The physical characteristics of the scaffold determine indeed, as well the biochemical factors, the fate of the cells. We use an innovative composite material consisting of hydrogel with different molecular weight and with suitable accordion-like and woodpile structures in order to tailor stiffness and elasticity conferred to the final structure.These novel 3D bioinspired scaffolds were obtained by both single- (1PP) and two-photon polymerization (2PP) processing. In particular, 2PP scaffolds represent a great advantage with respect to previous achievements based on traditional methods. 3D-structures were fabricated with lateral resolution of some microns, allowing an advanced control of pore microarchitecture of defined tensile strength, and the inclusion of albumin microspheres with various functionalities. The morphological, biochemical and functional characteristics are discussed. Moreover, the effects of the structured hydrogel scaffolds on the proliferation and differentiation of adult stem cells is analyzed in view of the fabrication of portion of contractile cardiac muscle to be obtained In Vitro.

Tuning the refractive index in 3D direct laser writing lithography: towards GRIN microoptics

AbstractWe report a study of the determination of polymer cross‐linking, namely the degree of conversion and refractive index of the microstructures created by two‐photon polymerization (TPP). The influence of TPP processing parameters such as laser intensity and scanning velocity is investigated. The degree of conversion is analyzed via Raman microspectroscopy and the refractive index is measured with the interferometric technique employing a Michelson interferometer. Moreover, the relationship between these two properties is revealed and details are discussed. The largest refractive index change that we have obtained is of the order of 10−2. Finally, we propose and demonstrate experimentally the realization of the gradient‐index (GRIN) structure, resulting from a laser‐induced local refractive index modification due to monomer cross‐linking, i.e. degree of conversion. This work implies that the TPP technique is a valuable tool for the fabrication of GRIN microoptics for (in)homogeneous molding of light flow at the micrometer scale. image

Study of the two-photon excitation of photoinitiator in various solvents, and the two-photon polymerization process.

In this study, the two-photon absorption excited fluorescence of the photosensitizer 4,4'-Bis(diethylamino)benzophenonin in different solvents is investigated by using mode-locked Ti:sapphire excitation having a wavelength of 800nm with pulse duration of 150fs at the rate of 1kHz. The fluorescence signals excited by wavelengths of 800 and 400nm have been compared. Contribution of these cross-section measurements for the two-photon polymerization processes is also reported.

Laser-based micro/nanofabrication in one, two and three dimensions

Advanced micro/nanofabrication of functional materials and structures with various dimensions represents a key research topic in modern nanoscience and technology and becomes critically important for numerous emerging technologies such as nanoelectronics, nanophotonics and micro/nanoelectromechanical systems. This review systematically explores the non-conventional material processing approaches in fabricating nanomaterials and micro/nanostructures of various dimensions which are challenging to be fabricated via conventional approaches. Research efforts are focused on laser-based techniques for the growth and fabrication of one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) nanomaterials and micro/nanostructures. The following research topics are covered, including: 1) laser-assisted chemical vapor deposition (CVD) for highly efficient growth and integration of 1D nanomaterial of carbon nanotubes (CNTs), 2) laser direct writing (LDW) of graphene ribbons under ambient conditions, and 3) LDW of 3D micro/nanostructures via additive and subtractive processes. Comparing with the conventional fabrication methods, the laser-based methods exhibit several unique advantages in the micro/nanofabrication of advanced functional materials and structures. For the 1D CNT growth, the laser-assisted CVD process can realize both rapid material synthesis and tight control of growth location and orientation of CNTs due to the highly intense energy delivery and laser-induced optical near-field effects. For the 2D graphene synthesis and patterning, room-temperature and open-air fabrication of large-scale graphene patterns on dielectric surface has been successfully realized by a LDW process. For the 3D micro/nanofabrication, the combination of additive two-photon polymerization (TPP) and subtractive multi-photon ablation (MPA) processes enables the fabrication of arbitrary complex 3D micro/nanostructures which are challenging for conventional fabrication methods. Considering the numerous unique advantages of laser-based techniques, the laser-based micro/nanofabrication is expected to play a more and more important role in the fabrication of advanced functional micro/nano-devices.

Towards integration of a liquid-filled fiber capillary for supercontinuum generation in the 1.2-2.4 μm range.

We demonstrate supercontinuum generation in unspliced as well as in integrated CS(2)-filled capillary fibers at different pump wavelengths of 1030 nm, 1510 nm, and 1685 nm. A novel method for splicing a liquid-filled capillary fiber to a standard single-mode optical fiber is presented. This method is based on mechanical splicing using a direct-laser written polymer ferrule using a femtosecond two-photon polymerization process. We maintain mostly single-mode operation despite the multi-mode capability of the liquid-filled capillaries. The generated supercontinua exhibit a spectral width of over 1200 nm and 1000 nm for core diameters of 5 μm and 10 μm, respectively. This is an increase of more than 50 percent compared to previously reported values in the literature due to improved dispersion properties of the capillaries.

Projection two-photon polymerization using a spatial light modulator

The development of a high-efficiency projection two-photon polymerization (P2PP) process by using a liquid crystal spatial light modulator (SLM) is presented. Rapid fabrication of 2D patterned microstructures with P2PP is demonstrated, and the effect of laser pattern and exposure dose on the surface roughness of the fabricated microstructures is investigated. It is found that the distribution of laser intensity at the focal plane of objective has a significant effect on the profiles of microstructures. This unique technology has a promising approach to increase the efficiency of two-photon polymerization (2PP) and a parallel fabrication of complex 2D and 3D microstructures.

Ultrafast lasers—reliable tools for advanced materials processing

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.

Two-Photon Polymerization of Polyethylene Glycol Diacrylate Scaffolds with Riboflavin and Triethanolamine used as a Water-Soluble Photoinitiator

In this study, the suitability of a mixture containing riboflavin (vitamin B2) and triethanolamine (TEOHA) as a novel biocompatible photoinitiator for two-photon polymerization (2PP) processing was investigated. Polyethylene glycol diacrylate was crosslinked using Irgacure(®) 369, Irgacure 2959 or a riboflavin-TEOHA mixture; biocompatibility of the photopolymer extract solutions was subsequently assessed via endothelial cell proliferation assay, endothelial cell viability assay and single-cell gel electrophoresis (comet) assay. Use of a riboflavin-TEOHA mixture as a photoinitiator for 2PP processing of a tissue engineering scaffold and subsequent seeding of this scaffold with GM-7373 bovine aortic endothelial cells was also demonstrated. The riboflavin-TEOHA mixture was found to produce much more biocompatible scaffolds than those produced with Irgacure 369 or Irgacure 2959. The results suggest that riboflavin is a promising component of photoinitiators for 2PP fabrication of tissue engineering scaffolds and other medically relevant structures (e.g., biomicroelectromechanical systems).

Structured Metal Film as a Perfect Absorber

A new type of absorber, a four-tined fish-spear-like resonator (FFR), constructed by the two-photon polymerization process, is reported. An absorbance of more than 90% is experimentally realized and the resonance occurs in the space between the tines. Since a continuous layer of metallic thin film covers the structure, it is perfectly thermo- and electroconductive, which is the mostly desired feature for many applications.

Three-dimensional sub-wavelength fabrication by integration of additive and subtractive femtosecond-laser direct writing

ABSTRACTAdditive nanofabrication by two-photon polymerization (TPP) has recently drawn increased attention due to its sub-100 nm resolution and truly three-dimensional (3D) structuring capability. However, besides additive processes, subtractive process is also demanded for many 3D fabrications. Method possessing both additive and subtractive fabrication capabilities was rarely reported. In this study, we developed a complementary 3D micro/nano-fabrication process by integrating both additive two-photon polymerization (TPP) and subtractive multi-photon ablation (MPA) into a single platform of femtosecond-laser direct writing process. Functional device structures were successfully fabricated including: polymer fiber Bragg gratings containing periodic holes of 500-nm diameter and 3D micro-fluidic systems containing arrays of channels of 1-µm diameter. The integration of TPP and MPA processes enhances the nanofabrication efficiency and enables the fabrication of complex 3D micro/nano-structures that are impractical to produce by either TPP or MPA alone, which is promising for a wide range of applications including integrated optics, metamaterials, MEMS, and micro-fluidics.