Two-photon polymerization (2PP), a 3D nano to microscale additive manufacturing process, is being used for the first time to fabricate small custom experimental packages (“targets”) to support laser-driven high-energy-density (HED) physics research. Of particular interest is the use of 2PP to deterministically print low-density, low atomic-number (CHO) polymer matrices (“foams”) at millimeter scale with sub-micrometer resolution. Deformation during development and drying of the foam structures remains a challenge when using certain commercial photo-resins; here we compare use of acrylic resins IP-S and IP-Dip. The mechanical strength of polymeric beam and foam structures is examined particularly the degree of deformation that occurs during the development and drying processes. The magnitude of the shrinkage in the two resins in quantified by printing sample structures and by use of FEA to simulate the deformation. Capillary drying forces are shown to be small and likely below the elastic limit of the core foam structure. In contrast the substantial shrinkage in IP-Dip (~5-10%) cause large shear stresses and associated plastic deformation particularly near constrained boundaries such as the substrate and locations with sharp density variation. The inherent weakness of stitching boundaries is also evident and in certain cases can lead to delamination. Use of IP-S shows marked reduction in deformation with a minor loss of print resolution
Precise assembly of carbon nanotubes (CNTs) in arbitrary 3D space with proper alignment is critically important and desirable for CNT applications but still remains as a long-standing challenge. Using the two-photon polymerization (TPP) technique, it is possible to fabricate 3D micro/nanoscale CNT/polymer architectures with proper CNT alignments in desired directions, which is expected to enable a broad range of applications of CNTs in functional devices. To unleash the full potential of CNTs, it is strategically important to develop TPP-compatible resins with high CNT concentrations for precise assembly of CNTs into 3D micro/nanostructures for functional device applications. We investigated a thiol grafting method in functionalizing multiwalled carbon nanotubes (MWNTs) to develop TPP-compatible MWNT-thiol-acrylate (MTA) composite resins. The composite resins developed had high MWNT concentrations up to 0.2 wt%, over one order of magnitude higher than previously published work. Significantly enhanced electrical and mechanical properties of the 3D micro/nanostructures were achieved. Precisely controlled MWNT assembly and strong anisotropic effects were confirmed. Microelectronic devices made of the MTA composite polymer were demonstrated. The nanofabrication method can achieve controlled assembly of MWNTs in 3D micro/nanostructures, enabling a broad range of CNT applications, including 3D electronics, integrated photonics, and micro/nanoelectromechanical systems (MEMS/NEMS).
Two-photon polymerization (TPP) is of increasing interest due to its unique combination of truly three-dimensional (3D) fabrication capability and ultrahigh spatial resolution of ~40 nm. However, the stringent requirements of non-linear resins seriously limit the material functionality of 3D printing via TPP. Precise fabrication of 3D micro/nanostructures with multi-functionalities such as high electrical conductivity and mechanical strength is still a long-standing challenge. In this work, TPP fabrication of arbitrary 3D micro/nanostructures using multi-walled carbon nanotube (MWNT)-thiolacrylate (MTA) composite resins has been developed. Up to 0.2 wt% MWNTs have been incorporated into thiol-acrylate resins to form highly stable and uniform composite photoresists without obvious degradation for one week at room temperature. Various functional 3D micro/nanostructures including woodpiles, micro-coils, spiral-like photonic crystals, suspended micro-bridges, micro-gears and complex micro-cars have been successfully fabricated. The MTA composite resin offers significant enhancements in electrical conductivity and mechanical strength, and on the same time, preserving high optical transmittance and flexibility. Tightly controlled alignment of MWNTs and the strong anisotropy effect were confirmed. Microelectronic devices including capacitors and resistors made of the MTA composite polymer were demonstrated. The 3D micro/nanofabrication using the MTA composite resins enables the precise 3D printing of micro/nanostructures of high electrical conductivity and mechanical strength, which is expected to lead a wide range of device applications, including micro/nano-electromechanical systems (MEMS/NEMS), integrated photonics and 3D electronics.
Two-photon polymerization (TPP) is a promising micro/nanofabrication technique, which is capable of fabricating 3D micro/nanostructures beyond the diffraction limit of light. However, the study of TPP process with a focus on the dependence of degree of conversion on TPP parameters using a non-destructive and efficient method is still lacking. We studied the quantitative relationships between the TPP parameters and the cross-linking of an acrylic-based IP-L 780 photoresist via systematic Raman characterization. The differences in the Raman spectra between the non-polymerized and the polymerized IP-L 780 photoresists were observed by probing the excitation of carbon-carbon double bond (C=C) vibrations. We obtained the relationship between the degree of conversion in TPP and the Raman spectra of the IP-L 780 resin, in which the intensity of the characteristic Raman peak of IP-L 780 at 1635 cm-1 decreases with the increase of the TPP laser dose. A mathematic model of the degree of conversion with respective to the TPP parameters, including laser average power and writing speed, has been established. The method provides a simple and effective way to characterize and optimize the TPP micro/nanofabrication processes. The established model for the degree of conversion as the function of TPP parameters will contribute to the advanced 3D TPP micro/nanofabrication by providing a guidance to optimize the laser doses, voxel sizes, and the mechanical strength of the polymers.
A technique was developed to achieve enhanced coherent anti-Stokes Raman scattering (CARS) imaging using selfassembled silica microspheres. In this study, a layer of optically transparent silica microspheres was self-assembled onto polymer grating samples to enhance the CARS signals. The highest enhancement of 12.5 was achieved using 6.1-μmdiameter microspheres for C-H molecule vibration. Finite-difference time-domain (FDTD) algorithm under the perfectly matched layer boundary condition was used to simulate the enhancement using silica microspheres of different diameters.
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