Aryltriazene Photopolymers for UV-Laser Applications: Improved Synthesis and Photodecomposition Study

An improved synthesis of photosensitive homopolymers containing aryltriazene chromophores covalently incorporated into the polymer backbone is reported. Such photopolymers proved to have promising properties for novel UV-laser applications. A homologous series of new aryltriazene polymers with increasingly branched side chains (R = Me, Et, iPr, tBu) was synthesized and characterized. Homogeneous thin films with thicknesses from ≈15 to >150 nm were prepared by spin-coating. Photodecomposition was studied in solution and on thin films. Polymers with increasingly branched and bulky substituents showed decreasing photodissociation rates. NMR studies suggested an enhanced hindrance of the N(2)–N(3) bond rotation in the aryltriazene moiety with increasing steric demand of the substituents.

[1]  D. Papazoglou,et al.  Direct Transfer and Microprinting of Functional Materials by Laser-Induced Forward Transfer , 2006 .

[2]  J. Tour,et al.  Preparative fluorous mixture synthesis of diazonium-functionalized oligo(phenylene vinylene)s. , 2005, The Journal of organic chemistry.

[3]  H. Fukumura Laser molecular implantation into polymer solids induced by irradiation below ablation threshold , 1997 .

[4]  W. Ehrfeld,et al.  Synthesis of Polysulfides Containing the Triazeno Group and Their Application as Photoresists in Excimer Laser Polymer Ablation , 1997 .

[5]  O. Nuyken,et al.  Synthesis and photoreactions of polyesters containing triazene and cinnamylidene malonyl units , 2000 .

[6]  Cheng-Kuo Sung,et al.  Fabrication of carbon nanotube field emission cathodes in patterns by a laser transfer method , 2006 .

[7]  T. Lippert Laser application of polymers , 2004 .

[8]  Ulrich Kogelschatz,et al.  UV excimer radiation from dielectric-barrier discharges , 1988 .

[9]  J A Barron,et al.  Biological Laser Printing: A Novel Technique for Creating Heterogeneous 3-dimensional Cell Patterns , 2004, Biomedical microdevices.

[10]  A. Wokaun,et al.  Photolysis, thermolysis, and protolytic decomposition of a triazene polymer in solution , 1995 .

[11]  Byung Doo Chin,et al.  Enhanced Luminance of Blue Light‐Emitting Polymers by Blending with Hole‐Transporting Materials , 2003 .

[12]  Martin B. Wolk,et al.  Laser thermal patterning of OLED materials , 2004, SPIE Optics + Photonics.

[13]  T. Lippert Interaction of Photons with Polymers: From Surface Modification to Ablation , 2005 .

[14]  Thomas Lippert,et al.  Chemical and spectroscopic aspects of polymer ablation: special features and novel directions. , 2003, Chemical reviews.

[15]  C. Rüchardt,et al.  Der mechanismus der Bachmann-Gomberg reaktion , 1964 .

[16]  A. Wokaun,et al.  Synthesis and characterization of a novel photosensitive triazene polymer , 1993 .

[17]  U. Kogelschatz,et al.  Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation , 1990 .

[18]  K. Eichhorn,et al.  Imagewise Structuring of Diazosulfonate Polymer Films by UV Light and Laser Irradiation - A Comparison , 2001 .

[19]  A. Wokaun,et al.  Synthesis and characterization of novel triazeno‐group containing photopolymers , 1995 .

[20]  A. Wokaun,et al.  Developing novel photoresists: microstructuring of triazene containing copolyester films , 1998 .

[21]  T. Lippert,et al.  Laser induced molecular transfer using ablation of a triazeno-polymer , 1998 .

[22]  Costas Fotakis,et al.  Time resolved schlieren study of sub-pecosecond and nanosecond laser transfer of biomaterials , 2005 .

[23]  D. Enders,et al.  A triazene-based new photolabile linker in solid phase chemistry , 2004 .

[24]  A. Holmes,et al.  Sacrificial layer process with laser-driven release for batch assembly operations , 1998 .

[25]  Maria Dinescu,et al.  Excimer laser forward transfer of mammalian cells using a novel triazene absorbing layer , 2006 .

[26]  J. Li,et al.  Name Reactions: A Collection of Detailed Reaction Mechanisms , 2002 .

[27]  A. Wokaun,et al.  Novel Laser Ablation Resists for Excimer Laser Ablation Lithography. Influence of Photochemical Properties on Ablation , 2001 .

[28]  M. Haley,et al.  Triazenes: a versatile tool in organic synthesis. , 2002, Angewandte Chemie.

[29]  A. Wokaun,et al.  Synthesis and properties of new photosensitive triazene polyacrylates , 2006 .

[30]  A. Oehlschlager,et al.  NMR study of hindered rotation in 1-aryl-3,3-dimethyltriazenes , 1968 .

[31]  H. Komber,et al.  Hyperbranched Poly(triazene ester)s as Novel Globular Photolabile and Thermolabile Polymers , 2001 .

[32]  W. Bachmann,et al.  THE SYNTHESIS OF BIARYL COMPOUNDS BY MEANS OF THE DIAZO REACTION , 1924 .

[33]  A. Wokaun,et al.  NMR studies of hindered rotation and thermal decomposition of novel 1‐aryl‐3,3‐dialkyltriazenes , 1992 .

[34]  R. A. McGill,et al.  Laser deposition of polymer and biomaterial films. , 2003, Chemical reviews.

[35]  A. Wokaun,et al.  Polymers with Triazene Units in the Main Chain , 1995 .

[36]  Douglas B. Chrisey,et al.  Time-resolved study of absorbing film assisted laser induced forward transfer of Trichoderma longibrachiatum conidia , 2005 .

[37]  J. M. Fernández-Pradas,et al.  Laser-induced forward transfer of biomolecules , 2004 .

[38]  V. Niculescu,et al.  Synthesis and properties of new polyurethane ionomers. I. Photosensitive cationomers with triazene units , 2003 .

[39]  O. Nuyken,et al.  Azo-group-containing polymers for use in communications technologies , 1997 .

[40]  T. Lippert,et al.  Synthesis and characterisation of new hard polyurethanes with triazene pendants , 2005 .

[41]  B R Ringeisen,et al.  Generation of mesoscopic patterns of viable Escherichia coli by ambient laser transfer. , 2002, Biomaterials.