Polymerization Kinetics in Three‐Dimensional Direct Laser Writing

By in-situ measuring the scattered light during microstructure formation, the polymerization kinetics of three-dimensional direct laser writing are investigated in detail. Oxygen quenching, oxygen diffusion, and inhibitor depletion are shown to have substantial impact on the kinetic behavior. For typical photoresists based on multifunctional acrylates, the polymerization occurs in less than a millisecond.

[1]  E. Andrzejewska.  Photopolymerization kinetics of multifunctional monomers , 2001 .

[2]  Yang Gao,et al.  Two-photon polymerization: investigation of chemical and mechanical properties of resins using Raman microspectroscopy. , 2014, Optics letters.

[3]  Robert R McLeod,et al.  Radical diffusion limits to photoinhibited superresolution lithography. , 2013, Physical chemistry chemical physics : PCCP.

[4]  A. Piskarskas,et al.  Ultrafast laser nanostructuring of photopolymers: a decade of advances , 2013 .

[5]  M. Wegener,et al.  On three-dimensional dilational elastic metamaterials , 2013, 1310.3719.

[6]  C. Bowman,et al.  Reaction Diffusion Enhanced Termination in Polymerizations of Multifunctional Monomers , 1993 .

[7]  Martin Wegener,et al.  Direct laser writing of three-dimensional submicron structures using a continuous-wave laser at 532 nm , 2010 .

[8]  Andreas Tünnermann,et al.  Materials and technologies for fabrication of three-dimensional microstructures with sub-100 nm feature sizes by two-photon polymerization , 2012 .

[9]  Martin Wegener,et al.  Three-dimensional direct laser writing inspired by stimulated-emission-depletion microscopy [Invited] , 2011, 1105.5703.

[10]  A. Diaspro,et al.  Photopolymerization Inhibition Dynamics for Sub-Diffraction Direct Laser Writing Lithography , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[11]  Satoshi Kawata,et al.  Improving spatial resolution of two-photon microfabrication by using photoinitiator with high initiating efficiency , 2007 .

[12]  In-situ local temperature measurement during three-dimensional direct laser writing , 2013 .

[13]  G. Kim,et al.  Three-dimensional direct laser writing inspired by stimulated-emission-depletion microscopy , 2013 .

[14]  Bin Zhang,et al.  Improvement of the diffraction properties in holographic polymer dispersed liquid crystal bragg gratings , 2003 .

[15]  Kurt Busch,et al.  Three‐Dimensional Nanostructures for Photonics , 2010 .

[16]  Christopher N. Bowman,et al.  Modeling the Effect of Oxygen on Photopolymerization Kinetics , 2006 .

[17]  R. Liska,et al.  Strategies to reduce oxygen inhibition in photoinduced polymerization. , 2014, Chemical reviews.

[18]  Jaroslaw Jacak,et al.  120 nm resolution and 55 nm structure size in STED-lithography. , 2013, Optics express.

[19]  K. Moussa,et al.  Real-time kinetic study of laser-induced polymerization , 1989 .

[20]  Christian Decker,et al.  Kinetic approach of oxygen inhibition in ultraviolet- and laser-induced polymerizations , 1985 .

[21]  R. Gattass,et al.  Achieving λ/20 Resolution by One-Color Initiation and Deactivation of Polymerization , 2009, Science.

[22]  Alexander Penlidis,et al.  A Comprehensive Simulator/Database Package for Reviewing Free-Radical Homopolymerizations , 1996 .

[23]  Alexandra M. Greiner,et al.  Three‐Dimensional Microscaffolds Exhibiting Spatially Resolved Surface Chemistry , 2013, Advanced materials.

[24]  C. Decker.  Kinetic Study and New Applications of UV Radiation Curing , 2002 .

[25]  Nikita M. Bityurin,et al.  Spatial resolution in polymerization of sample features at nanoscale , 2007 .

[26]  Panos S. Shiakolas,et al.  Modeling of temperature-dependent diffusion and polymerization kinetics and their effects on two-photon polymerization dynamics , 2008 .

[27]  C. Bowman,et al.  Polymerization kinetics and volume relaxation behavior of photopolymerized multifunctional monomers producing highly crosslinked networks , 1994 .

[28]  C. Bowman,et al.  Development of a comprehensive free radical photopolymerization model incorporating heat and mass transfer effects in thick films , 2002 .

[29]  C. Decker,et al.  Photoinitiated crosslinking polymerisation , 1996 .

[30]  C. Bowman,et al.  Principles of voxel refinement in optical direct write lithography , 2011 .

[31]  J. Fischer,et al.  Three-dimensional multi-photon direct laser writing with variable repetition rate. , 2013, Optics express.

[32]  C. Fotakis,et al.  Diffusion-assisted high-resolution direct femtosecond laser writing. , 2012, ACS nano.

[33]  Shoji Maruo,et al.  Recent progress in multiphoton microfabrication , 2008 .