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Direct laser writing (DLW) via two-photon polymerization (TPP) has been established as a powerful technique for fabrication and integration of nanoscale components, as it enables the production of three dimensional (3D) micro/nano objects. This technique has indeed led to numerous applications, including micro- and nanoelectromechanical systems (MEMS/NEMS), metamaterials, mechanical metamaterials and photonic crystals. However, as the feature sizes decrease, an urgent demand has emerged to uncover the mechanics of nanosized polymer materials. Here, we fabricate coil spring shaped polymer nanowires using DLW via two-photon polymerization. We find that even the nanocoil springs follow a linear-response against applied forces, following Hooke’s law, as revealed by compression tests using an atomic force microscope. Further, the elasticity of the polymer material is found to become significantly greater as the wire radius is decreased from 550 to 350 nm. Polarized Raman spectroscopy measurements show that polymer chains are aligned in nanowires along the axis, which may be responsible for the size dependence. Our findings provide insight into the nanomechanics of polymer materials fabricated by DLW, which leads to further applications based on nanosized polymer materials.

Two-photon lithography allows us to fabricate arbitrary three-dimensional structures with micro/nano-spatial resolution. The intrinsic three-dimensional spatial resolution of two-photon lithography is a promising tool for developing a variety of novel photonic and mechanical nano-devices. In addition, two-photon lithography makes it possible to study the properties of polymers of micro/nano-meter dimension [1-4]. In this presentation, we show the evidence that the elasticity and the transition temperature of polymers start to show size-dependent characteristics when the size of the polymer decreases down to a few hundreds of nanometers. We fabricated free-standing polymer nano-wires in the shape of coil spring by two-photon lithography, and measured the elasticity of the nano-wires by applying a mechanical tension onto the springs through laser trapping technique under temperature control. From the stretching length of the spring generated by a certain optical force, the spring constant of the spring and the shear modulus of polymer were calculated from simple Hook’s law. The material we used is a compound of methyl-methacrylate, dipentaerythritol hexaacrylate, benzil, and 2-benzyl-2-(dimethylamino)-4’-morpholino-butyrophenone. We scanned a light spot of a Ti:Sapphire laser at 780 nm with a pulse width of 80 fs focused by a 1.4 NA microscope objective to shape the polymer nano-wires suspended by a thick pillar. We observed that the elasticity of the polymer, which is usually an invariable coefficient, changes according to the thickness of the polymer wire. Furthermore, we changed the temperature of the entire polymer structures from -20 to 40 °C with measuring the elasticity of the springs. We observed phase transition of polymer wires with a rapid change of the share modulus, which also shows a size-dependent behavior. Recently, the similar experimental results, i.e. the drop of the glass transition temperature, were also reported in thin polymer nano-films. Our result is a clear evidence of such a nano size-effect of mechanical properties in polymers confirmed from free-standing polymer nanostructures. [1]S. Nakanishi, H. Yoshikawa, S. Shoji, Z. Sekkat, and S. Kawata, J. Phys. Chem. B 112, 3586-3589 (2008). [2] S. Nakanishi, S. Shoji, S. Kawata, and H.-B. Sun, Appl. Phys. Lett. 91, 063112 (2007). [3]H. Ishitobi, S. Shoji, T. Hiramatsu, H.-B. Sun, Z. Sekkat, and S. Kawata, Opt. Express 16, 14106-14114 (2008). [4]S. Kawata, H.-B. Sun, T. Tanaka, and K. Takada, Nature, 412, 697 (2001).