NANOCOMPOSITE THIN FILMS: Assembly, Characterizations, & Applications Chaoyang Jiang Department of Chemistry The University of South Dakota St. Louis, June 26, 2008
Forest Products &Nanocomposite P. Monteiro@UC Berkeley
Nanocomposite Materials Synthesis Composite Wood Fiber Poly(Styrene-butadiene-styrene) (SBS) offers many of the properties of natural rubber, such as flexibility, high traction, and sealing abilities, with increased resistance to heat, weathering, and chemicals. S. Renneckar et.al. Cellulose, 2008, 15, 333. 3
Nanocomposite Materials Nanotechnology R&D Priority for the forest product NANOCOMPOSITE THIN FILMS: Assembly, Characterizations, & Applications 4
Layer by Layer Assembly Spin assisted LbL K. Char, et al. Adv. Mater. 2001, 13, 1076. H.-L. Wang, et al. Adv. Mater. 2001, 13, 1167. Spray assisted LbL G. Decher, et al. Science 1997, 277, 1232. J. B. Schlenoff et al. Langmuir 2000, 16, 9968. 5
Layer by Layer Assembly Rubner and Cohen MIT CEN, 2005, 83(38), 34. Saraf U Nebraska Science, 2006, 312, 1501. Kotov, U Michigan Nature Mater. 2003, 2(6), 413. 6
Layer by Layer Assembly Cellulose Nanowire (from Tunicate), 3-4 nm, CNW/PEI LbL films, Antireflective properties Kotov et.al. Langmuir 2007, 23, 7901. 7
Layer by Layer Assembly Lvov et.al. Biomacromolecules 2007, 8, 1987. calcium carbonate Employ cellulose microfibers as a support to fabricate bioactive composites with organized enzyme multilayer. The bio activity can be tuned by varying the number of enzyme layers. 8
Composite LbL Nanomembrane C. Jiang et al., Nature Mater.. 2004, 3(10), 721. S. Markutsya, et al. Adv. Funct. Mater., 2005, 15(5), 771 9
Free standing LbL Films a1 b1 a2 a3 c1 b2 c2 V. Kozlovskaya, et.al., Macromolecules 2005, 38, 4828. a4 c1 c2 C.Jiang, et.al. Adv. Mater. 2006, 18, 829. Y. G. Guo, et. al., Adv. Funct. Mater. 2005, 15, 196. 10
Biomimetic Approach Golay cell design of IR detector un-cooled biological receptors with 30mK sensitivity IR radiation Membrane V. V. Tsukruk, et al. Biomacromolecules, 2001, 2, 304. Temperature modulated pressure 11
Free standing LbL Thin Films Sacrificial Layer Acetone Spin-assisted LbL Sacrificial Layer method Freely Suspended LbL nanomembranes 12
Free standing LbL Thin Films ngn n = 3, 5, 7, 9, 11, 80 + - + - + - + (PAH-PSS) n PAH/Au/(PAH-PSS) n PAH 2 nm Thickness (nm) 60 40 20 C. Jiang, et al. Nature Mater. 2004, 3, 721. 0 0 4 8 12 Number of PAH-PSS bilayers 13
Nanomechanics Bulging Tests Laser SEM CCD Camera Pressure sensor C. Jiang, et al. Nature Mater. 2004, 3, 721. Range accuracy Deflection: 0-10 μm, ½ λ (~300 nm) Pressure: 100 kpa, 2 Pa 14
Bulging Test Membrane deflection 200 μm 15
Bulging Test Bulging results and elastic modulus Without Gold With Gold 400 μm Mechanical parameters for different freely suspended nanomembranes Membrane type and Gold content Fabricatio n method Membrane diameter (μm) Elastic modulus (GPa) 9G9, 3.9% SA-LbL 400 6.6±3.3 9G9, 0.5% SA-LbL 400 4.3±2.0 9_9, 0% SA-LbL 400 1.5±1.0 9G9, 4% LbL N/A * N/A* * Film was broken into small piece, which can not be transfer to holey substrate. P = C 0 E 1 ν 2 h a 4 4 + C 1 σ h a 2 0 2 d h + C 2 E h 1 ν a 4 4 d h 3 C. Jiang, et al. Nature Mater. 2004, 3, 721. 16
Micropattern in Nanomembrane Au NP C. Jiang, et al. Adv. Mater. 2005, 17, 1669. 17
Gold Nanoparticle Arrays 13 nm 6 nm 1 μm 1 μm 18
Localized Mechanical Testing 10 μm 30 μm Location λ (μm) E (GPa) With Gold 3.52 4.35 Without Gold 2.76 2.08 Elastic modulus C. M. Stafford, et al. Nature Mater. 2004, 3, 545. A. Nolte, et al. Macromolecules 2005, 38, 5367. C. Jiang, Nano Letters. 2006, 6, 2254. 19
SERS in Nanomembranes Confocal Raman microscope - Na + n Pump Pressure Sensor Sealed chamber Nanomembrane Laser 50/50 Beam splitter Notch filter CCD C.Jiang, et al. Adv. Mater. 2005, 17, 1669. 20
Polymer Chain Behavior 4000 Relative intensity 3500 3000 2500 2000 1500 1100 1200 1300 1400 1500 1600 1700 Raman shift (cm -1 ) 0 5 20 40 60 80 SO3 Raman shift (cm -1 ) 1592 1590 1588 1586 1584 1582 1580 1 2 3 4 5 0 2000 4000 6000 Deflection (nm) SO SO 3 3 C.Jiang, et al. Phys. Rev. Lett. 2005, 95, 115503. Chain-like Au-NP aggregation + spreading of polymer chains Bridging multiple nanoparticles through stretched backbones Outstanding mechanical properties of SA-LbL films 21
LbL film with Silver Nanowires 2.5% 15.0% R. Gunawidjaja, Adv. Funct. Mater. 2006, 16, 2024. Density of Silver nanowires can tune the mechanical properties of LbL thin films. 22
Buckling Patterns of Ag LbL Films 5 μm 20 μm Buckling patterns stop at the location where silver nanowire appears. 23
3D Nanomembranes Micro-sculptured nanomembranes < 200 nm 24
Optical Grading with 3D Nanofilm Y. Lin, et. al. Adv.Mater. 2007, 19, 3827.
Sensitive LbL Composites Films 26
Micromechanical Tests D1 C1 200μm Membrane Diameter (μm) Elastic Modulus (GPa) B1 200 5.3±0.4 100 5.6±0.2 A1 A2 A3 A4 75 6.3±1.0 2.5 50 6.8±1.2 Deflection (μm) 2.0 1.5 1.0 A1 A2 A3 A4 0.5 0.0 average fit 0 400 800 1200 1600 Pressure (Pa) C. Jiang, et al. Adv. Funct. Mater. 2006, 16, 27. 27
Microcavity Arrays Half-inch wafer 64 64 cavity array Over 4000 membranes 600μm 28
Uniform Thermal Behavior 29
Thermal Bulging Heat Cool Heat Cool 400 180 nm/k Deflection (nm) 200 0-200 -400 Experimental Finite Element Analysis 298 299 300 301 Temperature (K) C.Jiang, et al. Chem. Mater. 2006, 18, 2632. Finite Element Analysis 30
NIR Sensing Tests CCD Camera Light Laser 785 nm 50-150 mw Laser focus to 500 μm diameter 31
Applications for Nanofilms Develop multilayer ultra-thin membranes with more flexible polyelectrolyte to achieve higher sensitivity. Increase thermal isolation and design novel substrates for high resolution imaging application. Using SERS properties and design portable and sensitive chemical detector Infrared detector with ability to detect NIR radiations in different wavelength. Biological and medical application, eg. drug release and delivery. 32
Summary Layer-by-Layer assembly a versatile method in fabricating multilayer nanomembranes with a variety of nanoscale building blocks, including cellulose nanocrystals and other forest products. Surface-enhanced Raman spectroscopy Molecular information within the nanoscale composite thin film; confocal technique can provide spatial resolutions for composite nanomembranes Free-standing LbL nanomembranes with functional nanostructures are suitable for sensing applications in mechanical, thermal, and optical areas. 33
Acknowledgements NSF 05-06832 Bioinspired Flex Nanomembranes for Multifunctional Microsensors. Nanoscale Interdisciplinary Research Team (NIRT) Dr. Vladimir V. Tsukruk (GT) (PI) Dr. Zhiqun Lin (ISU) Dr. Nicholas A. Kotov (U Michigan) Dr. Chang Liu (UIUC/NW) Dr. Eugene Zubarev (Rice U) $$$ AFOSR, NASA, NSF, ARO. Forest Product Laboratory 34
Materials Chemistry @USD 35