An Epoxy Photoresist Modified by Luminescent Nanocrystals for the Fabrication of 3D High‐Aspect‐Ratio Microstructures

An epoxy-based negative-tone photoresist, which is known as a suitable material for high-aspect-ratio surface micromachining, is functionalized with red-light-emitting CdSe@ZnS nanocrystals (NCs). The proper selection of a common solvent for the NCs and the resist is found to be critical for the efficient incorporation of the NCs in the epoxy matrix. The NC-modified resist can be patterned by standard UV lithography down to micrometer-scale resolution, and high-aspect-ratio structures have been successfully fabricated on a 100 mm scaled wafer. The “as-fabricated”, 3D, epoxy-based surface microstructures show the characteristic luminescent properties of the embedded NCs, as verified by fluorescence microscopy. This issue demonstrates that the NC emission properties can be conveniently conveyed into the polymer matrix without deteriorating the lithographic performance of the latter. The dimensions, the resolution, and the surface morphology of the NC-modified-epoxy microstructures exhibit only minor deviations with respect to that of the unmodified reference material, as examined by means of microscopic and metrologic investigations. The proposed approach of the incorporation of emitting and non-bleachable NCs into a photoresist opens novel routes for surface patterning of integrated microsystems with inherent photonic functionality at the micro- and nanometer-scale for light sensing and emitting applications.

[1]  P. Renaud,et al.  SU8‐Silver Photosensitive Nanocomposite , 2004 .

[2]  Feng Hua,et al.  Ultrathin cantilevers based on polymer-ceramic nanocomposite assembled through layer-by-layer adsorption , 2004 .

[3]  G. Simon,et al.  Correlation between rheological, mechanical, and barrier properties in new copolyamide-based nanocomposite films , 2006 .

[4]  M. L. Curri,et al.  Optical properties of hybrid composites based on highly luminescent CdS nanocrystals in polymer , 2004 .

[5]  N. D. Rooij,et al.  Micromachined photoplastic probe for scanning near-field optical microscopy , 2001 .

[6]  Duncan W. McBranch,et al.  Electron and hole relaxation pathways in semiconductor quantum dots , 1999 .

[7]  P. Gómez‐Romero Hybrid Organic–Inorganic Materials—In Search of Synergic Activity , 2001 .

[8]  C. Shearwood,et al.  Mechanical properties and interfacial characteristics of carbon-nanotube-reinforced epoxy thin films , 2002 .

[9]  Miklós Zrínyi,et al.  Smart Nanocomposite Polymer Membranes with On/Off Switching Control , 2006 .

[10]  U. Suter,et al.  Polymer Nanocomposites Containing Superstructures of Self-Organized Platinum Colloids , 2001 .

[11]  Xiaogang Peng,et al.  Experimental Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals , 2003 .

[12]  Christopher B. Murray,et al.  Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies , 2000 .

[13]  Leon M Bellan,et al.  Electrospun polymer nanofibers as subwavelength optical waveguides incorporating quantum dots. , 2006, Small.

[14]  Peter Reiss,et al.  Highly Luminescent CdSe/ZnSe Core/Shell Nanocrystals of Low Size Dispersion , 2002 .

[15]  G. Somorjai,et al.  Surface Studies of Polymer Blends by Sum Frequency Vibrational Spectroscopy, Atomic Force Microscopy, and Contact Angle Goniometry , 1998 .

[16]  G. Kickelbick,et al.  Concepts for the incorporation of inorganic building blocks into organic polymers on a nanoscale , 2003 .

[17]  Young-Sik Park,et al.  Kinetics of Cationic Photopolymerizations of UV‐Curable Epoxy‐Based SU8‐Negative Photoresists With and Without Silica Nanoparticles , 2006 .

[18]  Rupali Gangopadhyay and,et al.  Conducting Polymer Nanocomposites: A Brief Overview , 2000 .

[19]  G. Kim,et al.  Micropositioning and microscopic observation of individual picoliter-sized containers within SU-8 microchannels , 2007 .

[20]  Vincent M. Rotello,et al.  Polymer‐Mediated Nanoparticle Assembly: Structural Control and Applications , 2005 .

[21]  Louis E. Brus,et al.  Luminescence Photophysics in Semiconductor Nanocrystals , 1999 .

[22]  Francesca Campabadal,et al.  Wafer level packaging of silicon pressure sensors , 2000 .

[23]  Zhiyong Tang,et al.  Multicolor luminescence patterning by photoactivation of semiconductor nanoparticle films. , 2003, Journal of the American Chemical Society.

[24]  Nitin Kumar,et al.  High-performance elastomeric nanocomposites via solvent-exchange processing. , 2007, Nature materials.

[25]  Anna C. Balazs,et al.  Nanoparticle Polymer Composites: Where Two Small Worlds Meet , 2006, Science.

[26]  W. Caseri,et al.  Preparation, structure and properties of uniaxially oriented polyethylene-silver nanocomposites , 1999 .

[27]  E. Sargent,et al.  Photoconductivity from PbS-nanocrystal∕semiconducting polymer composites for solution-processible, quantum-size tunableinfrared photodetectors , 2004 .

[28]  Jae-Wook Kang,et al.  Simple and Low Cost Fabrication of Thermally Stable Polymeric Multimode Waveguides using a UV-curable Epoxy , 2003 .

[29]  Gregory D. Scholes,et al.  Surface passivation in CdSe nanocrystal–polymer films revealed by ultrafast excitation relaxation dynamics , 2004 .

[30]  Hariharan Srikanth,et al.  Superparamagnetic Polymer Nanocomposites with Uniform Fe3O4 Nanoparticle Dispersions , 2006 .

[31]  Tomokazu Yoshimura,et al.  Antioxidant action by gold-PAMAM dendrimer nanocomposites. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[32]  Andreas Kornowski,et al.  One-pot synthesis of highly luminescent CdSe/CdS core-shell nanocrystals via organometallic and greener chemical approaches , 2003 .

[33]  David R. Lide,et al.  Handbook of Organic Solvents , 1995 .

[34]  Jost Goettert,et al.  Functional Micro Devices Using 'Nanoparticle-Photoresist' Composites , 2003, Int. J. Comput. Eng. Sci..

[35]  P. Renaud,et al.  Conductive SU8 Photoresist for Microfabrication , 2005 .

[36]  Hengpeng Wu,et al.  Organic–Inorganic Nanocomposites: Unique Resists for Nanolithography , 2001 .

[37]  Louis E. Brus,et al.  Electronic properties of CdSe nanocrystals in the absence and presence of a dielectric medium , 1999 .

[38]  V. Bulović,et al.  Color-saturated green-emitting QD-LEDs. , 2006, Angewandte Chemie.

[39]  Bruce M. Novak,et al.  Hybrid nanocomposite materials―between inorganic glasses and organic polymers , 1993 .

[40]  M. L. Curri,et al.  Spontaneous emission control of colloidal nanocrystals using nanoimprinted photonic crystals , 2007 .

[41]  Vijay K. Varadan,et al.  Chemical bonding of multiwalled carbon nanotubes to SU-8 via ultrasonic irradiation , 2003 .

[42]  Peter Vettiger,et al.  High-aspect-ratio, ultrathick, negative-tone near-UV photoresist and its applications for MEMS , 1998 .

[43]  R. Zentel,et al.  Semiconductor nanocrystals with multifunctional polymer ligands. , 2003, Journal of the American Chemical Society.

[44]  Justin M. Hodgkiss,et al.  Blue semiconductor nanocrystal laser , 2005 .

[45]  S. Wuister,et al.  Local-field effects on the spontaneous emission rate of CdTe and CdSe quantum dots in dielectric media. , 2004, The Journal of chemical physics.

[46]  John A. Ripmeester,et al.  The Effect of Dispersion Media on Photoluminescence of Colloidal CdSe Nanocrystals Synthesized from TOP , 2005 .

[47]  M. Toney,et al.  Structure and interaction of organic/inorganic hybrid nanocomposites for microelectronic applications. 1. MSSQ/P(MMA-co-DMAEMA) nanocomposites , 2002 .

[48]  W. Cao,et al.  Fabrication and Characterization of Stable Ultrathin Film Micropatterns Containing CdS Nanoparticles , 2003 .

[49]  M. Tamborra,et al.  Hybrid nanocomposites based on CdS and CdSe colloidal nanocrystals in organic polymers , 2005, SPIE Microtechnologies.

[50]  Klavs F. Jensen,et al.  Full Color Emission from II–VI Semiconductor Quantum Dot–Polymer Composites , 2000 .

[51]  George M. Whitesides,et al.  Composite ferromagnetic photoresist for the fabrication of microelectromechanical systems , 2005 .

[52]  G. Scholes,et al.  Surface passivation of luminescent colloidal quantum dots with poly(dimethylaminoethyl methacrylate) through a ligand exchange process. , 2004, Journal of the American Chemical Society.

[53]  Vikram C. Sundar,et al.  Color-selective semiconductor nanocrystal laser , 2002 .

[54]  Alexander Eychmüller,et al.  Structure and Photophysics of Semiconductor Nanocrystals , 2000 .

[55]  N. V. van Hulst,et al.  Photoplastic near‐field optical probe with sub‐100 nm aperture made by replication from a nanomould , 2003, Journal of microscopy.

[56]  Xiaogang Peng,et al.  Control of photoluminescence properties of CdSe nanocrystals in growth. , 2002, Journal of the American Chemical Society.

[57]  N. D. Rooij,et al.  Soft, entirely photoplastic probes for scanning force microscopy , 1999 .