Abstract………………………………………….……………………………...........І Contents…………………………………………………………………………......V List of Tables ……………………………………………………………………. VIII List of Figures................….......................................................................................IX Chapter 1 Introduction…………………………………………………………..…1 1.1 Self-assembly………………………………………………………….……2 1.2 Development of Nanopatterning Technology………………………………7 1.2.1 Top-down Method…………………………………………………...…8 1.2.2 Button-up Method………………………………………………….…13 1.3 Nanopatterning from Self-assembly of Block Copolymer (BCP) ………..14 1.3.1 Solvent Evaporation-induced Orientation for BCP Self-assembly.......15 1.3.2 Nanoporous Templates from Degradable BCP Nanopatterns ………..17 1.3.3 Pore-filling Process for Nanoporous Template ……………………....20 1.3.3.1 Pore-filling nanoparticles by Solution Wetting…………………...20 1.3.3.2 Pore-filling Polymer by Melt Wetting …........................................22 1.3.3.3 Pore-filling Polymer by Solution Annealing ……………………..24 1.4 Applications of Nanoporous Templates for Semiconductors ……………...26 1.4.1 Quantum Confinement Effect in Semiconductors ……………........…28 1.4.2 Electronic and Optical Properties of CdS Nanocrystals ……...........…29 1.4.3 Applications of CdS Nanostructures ….................................................30 1.5 Nanoporous Templates for Drug Delivery ……….…....…………………..32 1.5.1 Organic Core/shell Nanospheres for Drug Delivery……….................32 1.5.2 Mesoporous Silica Nanoparticles for Drug Delivery…….............…...33 1.5.3 Ionic Membrane for Nanoscale Drug Delivery………………….........34 1.6 Nanoporous Templates for Optical Molecules, Pyrene……………………36 1.6.1 Photophysics of Pyrene Monomer and Excimer...................................36 1.6.2 Pyrene in Organized Media...................................................................38 1.6.3 Applications of Orientated Pyrene Nanostructures...............................39 1.7 Nanoporous Templates for Conjugated Polymers……..…………………..43 1.7.1 Photophysics of Poly(p-phenylenevinylene) (PPV).............................43 1.7.2 Nanosclae Spatial Effect on Oriented Conjugated Polymers...............45 1.7.3 Applications of Segmented PPV Nanostructures.................................47 Chapter 2 Objectives………………………………………………...............……50 Chapter 3 Experimental Methods..........................................................................54 3.1 Instrumentation............................................................................................54 3.2 Experimental Section...................................................................................54 3.2.1 Materials…………………………………………...............................54 3.2.2 Preparation of Nanoporous Templates……………….........................56 3.2.3 Pore-Filling Method by Wetting Effect……………................………56 3.2.4 Pore-Filling Method for Cd(II) by Capillary Force……..................…57 3.2.5 Pore-Filling Method for Sirolimus by Capillary Force…............……58 3.2.6 Pore-Filling of Pyrene and Pyrene/Isochromanone (PY/CM) by Solvent Annealing…………….................................................................…62 3.2.7 Pore-Filling of DP-PPV-PEO by Solvent Annealing ...........................63 Chapter 4 Results and Discussion ………………………………..................……70 4.1 Pore-filling of Gold Particles by Wetting Effect………............................…70 4.2 Pore-Filling Nanoporous Templates for CdS Nanoarrays ….................……75 4.2.1 Pore-Filling of CdS by Air-block Releasing………….................……75 4.2.2 Pore-Filling of CdS by Directed Capillary Force (method 1 & 2)....…77 4.2.3 Optical Properties of Templated Nanocrystals by Air-block Releasing...................................................................……….........................81 4.2.4 Optical Properties of Templated Nanocrystals by Directed Capillary Force (method 1&2)…...................................................................................83 4.3 Pore-Filling Nanoporous Templates for Nanoscale Drug Delivery…...........84 4.3.1 Characterization of Templated Sirolimus Nanoarrays…………......…85 4.3.2 Cumulative Release Profiles of Sirolimus……………………........…88 4.3.3 Mechanism of Diffusion Control for Cumulative Release Profiles......91 4.3.4 Results of Activity Assay of Sirolimus..........................................…...93 4.4 Pore-Filling Nanoporous Templates for PY/CM Nanoarrays on Dispersion.95 4.4.1 Characterization of Templated PY/CM Nanoarrays………………….95 4.4.2 Optical properties of Templated PY/CM Nanoarrays………………...96 4.4.3 Nanoscale Spatial Effect on Dispersion for Templated PY/CM Nanoarrays …...........................................................................................…101 4.5 Pore-Filling Nanoporous Templates for PY and PY/CM Nanoarrays on Molecular Orientation……………………………………………………........107 4.5.1 Characterization and Optical properties of Templated PY/CM Nanoarrays with various mixing ratios..............................................……..107 4.5.2 Induced Molecular Orientation of PY/CM within Nanoporous Template by Nanoscale Spatial Effect.........................................................................113 4.6 Pore-Filling Nanoporous Templates for DP-PPV-PEO (PVE) Nanoarrays.123 4.6.1 Characterization and Optical properties of Templated PVE Nanoarrays....................................................................................................124 4.6.2 Induced Chain Alignment of PPV-PEO within Nanoporous Template by Nanoscale Spatial Effect...............................................................................130 Chapter 5 Conclusions...........................................................................................136 Chapter 6 References .............................................................................................139 Publications………….............................................................................................151 List of Tables Table 3.1 Characteristics of PS-PLLA Block Copolymers.........................................56 Table 3.2 Characteristics of DP-PPV-PEO copolymers ..............................................65 Table 4.1 Loading contents (LC) of cylindrical nanoarrays and lamellar nanoarrays in different thicknesses ....................................................................................................91 Table 4.2 Comparison of the R = A1419/A846 of the GI-FTIR absorbance at 1419 cm-1 and 846 cm-1 for nanoporous PS template on PY/CM thin film with vatious mixing ratios before (Rbefore) and after (Rafter) solvent annealing…………………..............119 List of Figures Figure 1.1 Examples of static self-assembly. (a) Crystal structure of a ribosome. (b) Self-assembled peptideamphiphile nanofibers. (c) An array of millimeter sized polymeric plates assembled at a water/perfluorodecalin interface by capillary interactions. (d) Thin film of a nematic liquid crystal on an isotropic substrate. (e) Micrometersized metallic polyhedra folded from planar substrates. (f) A three-dimensional aggregate of micrometer plates assembled by capillary forces.......3 Figure 1.2 Examples of dynamic self-assembly. (a) An optical micrograph of a cell with fluorescently labeled cytoskeleton and nucleus; microtubules ~ 24 nm in diameter) are colored red. (b) Reaction-diffusion waves in a Belousov-Zabatinski reaction in a 3.5-inch Petri dish. (c) A simple aggregate of three millimeter-sized, rotating, magnetized disks interacting with one another via vortex-vortex interactions. (d) A school of fish. (e) Concentric rings formed by charged metallic beads 1 mm in diameter rolling in circular paths on a dielectric support. (f) Convection cells formed above a micropatterned metallic support. The distance between the centers of the cells is ~ 2 mm...............................................................................................................4 Figure 1.3 (a) Schematic phase diagram showing the various ‘classical’ BCP morphologies adopted by non-crystalline linear diblock copolymer. The blue component represents the minority phase and the matrix, majority phase surrounds it. (b) Schematic of morphologies for linear ABC triblock copolymer. A combination of block sequence (ABC, ACB, BAC), composition and block molecular weights provides an enormous parameter space for the creation of new morphologies. Microdomains are colored as shown by the copolymer strand at the top, with monomer types A, B and C confined to regions colored blue, red and green, respectively. (Reprinted with permission from Physics Today.12 Copyright (1999) American Institute of Physics)......................................................................................7 Figure 1.4 (a) Topographic nanopattern (b) Chemical nanopattern............................8 Figure 1.5 Photolithography. Outline of the procedures used for fabrication of nanostructures using topographically micropatterned materials. Trenches were formed by selective etching of regions of the substrate protected by disordered SAMs............................................................................................................................9 Figure 1.6 Schematic of metallic mask fabrication processes...................................10 Figure 1.7 An elastomeric stamp is made by casting a prepolymer of PDMS against a master that is usually made by microlithographic techniques. The stamp is inked with a solution of hexadecanethiol in ethanol, dried in a stream of N2, and then brought into contact with the gold surface. The patterned SAMs can be used as resists in wet chemical etching to transfer patterns to the Au film............................12 Figure 1.8 Schematic representation of DPN. A water meniscus forms between the AFM tip coated with ODT and the Au substrate. The size of the meniscus, which is controlled by relative humidity, affects the ODT transport rate, the effective tip-substrate contact area, and DPN resolution..........................................................13 Figure 1.9 SPM phase micrographs of PS-PEO with cylindrical microdomains oriented normal to the film surface are obtained after spin coating onto silicon substrate (a) 25K PS-PEO with a film thickness of 140 nm (b) 90K PS-PEO with film thickness of 150 nm............................................................................................16 Figure 1.10 The Schematic illustration of formation of PS-PLLA nanopattern prepared by spin coating............................................................................................17 Figure 1.11 FESEM image obtained from a thin film of P(S-b-MMA) after removal of the PMMA-block inside the cylinders, a) shows a top view, b) a cross-sectional view............................................................................................................................18 Figure 1.12 (a) Schematic cross-sectional view of a nanolithography template consisting of a uniform monolayer of PB spherical microdomains on silicon nitride. PB wets the air and substrate interfaces. (b) Schematic of the processing flow when an ozonated copolymer film is used, which produces holes in silicon nitride. (c) Schematic of the processing flow when an osmium-stained copolymer film is used, which produces dots in silicon nitride........................................................................19 Figure 1.13 The (a) top view and (b) cross-section view FESEM micrographs of spin-coated PS-PLLA (fPLLAv=0.26) thin films on silicon wafer from chlorobenzene at 50oC after hydrolysis..............................................................................................20 Figure 1.14 (a) Schematic diagram of depositing nanoparticles into nanoporous template by withdrawal of the template from a solution. (b) The photoluminescence of the nanoparticles-filled template demonstrate that a higher solution concentration in the dipping process gives template with higher emission singles..........................22 Figure 1.15 SEM of (A) Damaged tip of a PS nanotube protruding from a porous alumina membrane. (B) Ordered array of tubes from the same PS sample after complete removal of the template. (C) Array of PTFE tubes. (D) PMMA tubes......23 Figure 1.16 TEM images of (a) PAN-based CNTs and (b) PS-b-PAN-based porous CNTs from commercial AAO membrane. (c) WAXD pattern and (d) Raman spectrum of PAN-based CNTs from commercial AAO membrane (d~150–400 nm). The sample was stabilized at 250°C for 30 min under air and pyrolyzed at 600°C for 1 h under nitrogen......................................................................................................26 Figure 1.17 TEM images of Pd/PLA nanotubes after annealed at 200°C for (a) 5min and (b) 24 h. TEM images of Pd nanotubes prepared by annealing at 200°C for (c) 24 h and (d) 48 h within the porous template, and following the removal of PLA polymers. The pore diameters of wetting porous templates are 55 nm, except (c), where the pore diameter is 70 nm..............................................................................26 Figure 1.18 Illustrations representing system dimensionality d: (a) bulk semiconductors, 3D; (b) thin films, layer structures, quantum wells, 2D; (c) linear chain structures, quantum wires, 1D; (d) clusters, colloids, microcrystallites, nanocrystallites, quantum dots, 0D............................................................................28 Figure 1.19 Densities N(E) of states for (a) 3D, (b) 2D, (c) 1D and (d) 0D systems (corresponding to ideal cases)....................................................................................29 Figure 1.20 Absorption spectrum of CdS in aqueous solution: different particle size..............................................................................................................................30 Figure 1.21 TEM micrographs of microtomed sections of PS/CdS composite material showing control of the CdS particle size using PS templates: (a) PS1 (22-nm pore diameter), (b) PS2 (31-nm pore diameter), and (c) PS3 (45-nm pore size template).............................................................................................................31 Figure 1.22 (a) A typical SEM image of drug-loaded TATePEG-b-Chol nanoparticles. (b) release profile of ciprofloxacin lactate from the TATePEG-b-Chol nanoparticles in PBS (pH 7.4) at 37℃.......................................................................33 Figure 1.23 SEM images of titania nanotubular surfaces. Left) Cross-sectional view of mechanically fractured sample showing that the length of the tubes is approximately 400 nm. Center) Top view of nanotubular surface. Right) High-magnification top view of nanotubular surface showing the tube diameter of approximately 80nm...................................................................................................35 Figure 1.24 Fraction of total protein released from nanotubes filled with a) 200, b) 400, and c) 800 mg of BSA, and d) 200, e) 400, and f) 800 mg of LYS. The time point at which all the protein is released is indicated by the dotted line. Concentrations at these time points are significantly different from those for time points before, however, not significantly different from the time points after, p<0.05, n=3.............................................................................................................................36 Figure 1.25 Schematic potential energy diagrams for pyrene excimer formation in the absence of ground-state association (a) and with pyrene ground state association (b)...............................................................................................................................38 Figure 1.26 (a) Chemical structure of TQPP-12. Axes define transition dipole orientation, which is discussed in the later IR spectroscopy analysis. (b) TQPP-12 based on semiempirical (AM1) Hamiltonian calculation. Side chains are fully extended from core.....................................................................................................41 Figure 1.27 GIXD of M1 film. The primary out-of-plane (001) reflection is blocked by the beam stop of the instrument............................................................................41 Figure 1.28 (a) SEM image of the inter-digitated Au finger electrodes on SiO2/Si substrate. (b) the height and cross-sectional images of PYPA polycrystalline films. (c) Schematic illustration of the proposed PYPA orientation in spin-coated films. The layer adjoining the hydrophilic substrate is the phosphonic acid headgroup, and the one exposed to air is the pyrene endgroup. Inset: Molecular structure of PYPA.......42 Figure 1.29 Plot of a drain current IDS versus drain voltage VDS at various gate voltages VG from a bottom-contact OFET comprising the PYPA polycrystalline stacked film at 230 K. The gap width between the electrodes is 400 nm..................43 Figure 1.30 Schematic diagram of the structure of the PPV photodiodes.................44 Figure 1.31 SEM micrograph (a) and AFM image (b) of the rubbed PPV layer (30 nm) on glass/ITO/PPV(120nm).................................................................................46 Figure 1.32 a) Polarized electroluminescence from a two-layer OLED with the configuration ITO/PPV (120 nm)/rubbed PPV (30 nm)/tBu-PPQ (30 nm)/Al. b) I±V characteristics and brightness of the device...............................................................46 Figure 1.33 Mechanism of P3HT chain alignment due to polymer flow and interaction between P3HT side chain.........................................................................47 Figure 1.34 SEM images of PPV after being isolated from the filters: nanorods prepared in a polycarbonate filter membrane with nominal diameter of 10 nm........49 Figure 1.35 PL decays of bands 1, 2, and S in bulk PPV film and nanotubes referred to as nt1 and nt2 in the text. (a) Band 2-film; (b) band 1-film; (c) band 2-nanotube nt1; (d) band 1-nanotube nt1; (e) band S-nanotube nt1; (f) band S-nanotube nt2. Zero-time delay corresponds to the beginning of the streak camera sweep..........................................................................................................................49 Figure 3.1 Schematic illustration of pore-filling processes by (a) air-block releasing, (b) directed capillary force (method 1), and (c) directed capillary force (method 2)................................................................................................................................58 Figure 3.2 Schematic illustration of pore-filling process by directed capillary force. (a) PS-PLLA thin film; (b) PS nanoporous template from hydrolytic PS-PLLA thin film; (c) PS nanoporous template floated onto the surface of solution for pore-filling sirolimus; (d) templated sirolimus nanoarrays from pore-filling template................60 Figure 3.3 Schematic illustration of nanoporous PS template pore-filled by optical materials through solvent-annealing process. (a) PS-PLLA thin film; (b) nanoporous PS template from PS-PLLA thin film after hydrolysis; (c) nanoporous PS template floated on water surface and collected by optical materials coated glass slide; (d) nanoporous PS template on optical materials film coated glass slide for solvent-annealing process; (e) templated optical materials nanoarrays after solvent-annealing process..........................................................................................63 Figure 4.1 The tapping-mode SPM height images of the nanopatterning morphology for spin-coated PS–PLLA thin films on glass slide at ambient temperature (a) before; (b) after hydrolysis.....................................................................................................71 Figure 4.2 TEM mass-thickness images of hydrolyzed PS-PLLA templates immersed into Au solution (a) without and (b) with ultrasonic treatment for 30 min..............................................................................................................................71 Figure 4.3 TEM micrographs of pore-filling functional gold nanoparticles in hydrolyzed PS-PLLA templates after O2 plasma treatment with 75 Watt for 20 seconds.......................................................................................................................73 Figure 4.4 (a) The tapping-mode SPM height image of PS-PLLA template after hydrolysis 4 days and RuO4 staining for 30s. (b) Measured Contact angle image of H2O on stained PS template before and after RIE treatment with 20 Watt for 20 seconds.......................................................................................................................74 Figure 4.5 TEM micrographs of pore-filling functional gold nanoparticles in hydrolyzed PS-PLLA templates after O2 plasma treatment with 20 Watt and RuO4 staining for 30 seconds...............................................................................................74 Figure 4.6 (a) Air-extracting apparatus (b) Measured Contact angle image of H2O and methanol on PS templates...................................................................................76 Figure 4.7 (a) TEM image of CdS nanocrystals into hexagon cylinder (HC) template by air-block releasing. (b) Electron-diffraction pattern of the CdS particles.............77 Figure 4.8 TEM images of nanoporous template generated from cylindrical PS-PLLS diblock copolymer thin film. After pore-filling of CdAc2 by directed capillary force and surface washing, the HC CdS structure was achieved by adding equivalent amounts of H2S for 2 hr from (a) methanol solvent; (b) aqueous solvent. Inset shows the electron diffraction pattern of the CdS nanoparticles.......................80 Figure 4.9 TEM images of templated CdS nanoarrays through pore-filling processes by directed capillary force (method 2). Inset shows the selected area electron diffraction pattern from the central region of the sample...........................................80 Figure 4.10 TEM image of CdS nanoparticles by spin coating of 0.48M CdAc2 methanol solution and exposing to H2S vapor for 2 hours........................................82 Figure 4.11 PL spectra of CdS solid state and templated CdS through pore-filling processes by air-block releasing and directed capillary force (method 2). The exciting length is at 450 nm. Inset shows corresponding UV-vis absorption spectra........................................................................................................................82 Figure 4.12 Confocal microscopy image (excited at 454nm and detected from 480nm to 700nm) of (a) CdS solid state; (b) pore-filling of CdS into nanoporous template by air-block releasing; (c) pore-filling of CdS into nanoporous template by direct capillary force (method 2)................................................................................84 Figure 4.13 TEM images of (a) PS cylindrical nanoporous template from hydrolytic PS-PLLA film; (b) templated sirolimus-loaded cylindrical nanoarrays from pore-filling template; (c) PS lamellar nanoporous template from hydrolytic PS-PLLA film; (b) templated sirolimus-loaded lamellar nanoarrays from pore-filling template......................................................................................................................86 Figure 4.14 TEM images of PTA staining samples: (a) PS nanoporous template from hydrolytic PS-PLLA film; (b) templated sirolimus nanoarrays from pore-filling template......................................................................................................................87 Figure 4.15 FTIR spectra of templated sirolimus-loaded cylindrical nanoarrays before (dash dot line) and after (dot line) drug eluting. The solid line reveals the spectrum of pure sirolimus.........................................................................................88 Figure 4.16 (a) Cumulative release profiles of sirolimus from the sirolimus-loaded cylindrical nanoarrays (blue triangle), the sirolimus-loaded lamellar nanoarrays (green diamond), the AAO/sirolimus hybrids (black circle) and the PS/drug blends (red square). Inset shows the fitting curve (black line) of the sirolimus-loaded cylindrical nanoarrays. Minf : the infinite amount of loaded drugs in test templates; Mt: the cumulative amount of drug released at time t. (b) Schematic illustration of the sirolimus-loaded cylindrical nanoarrays, the AAO/sirolimus hybrids and the PS/drug blends...........................................................................................................89 Figure 4.17 SPM topography images of PS/drug blended matrix by (a) before and (b) after drug eluting process...........................................................................................89 Figure 4.18 Cumulative release profiles of sirolimus released from test nanoarrays in different thicknesses...............................................................................................91 Figure 4.19 Results of activity assay of sirolimus released from cylindrical or lamellar nanoarrays. Fluorescence microscopic images, showing viability of RASMC following treatment for three days with (a) fresh medium or collected medium that contained the sirolimus that was released from the (b) cylindrical or (c) lamellar nanoarrays....................................................................................................94 Figure 4.20 TEM images of (a) cylindrical nanoporous PS template from hydrolytic PS-PLLA thin film; (b) templated PY/CM nanoarrays with PTA staining................96 Figure 4.21 FL spectra of spin-coated PY/CM thin films on glass substrate (a) with; (b) without the deposition of nanoporous PS template before (solid line) and after (dot line) solvent annealing. Inset of (b) shows the enlarged scale of dot-line spectrum.....................................................................................................................97 Figure 4.22 (a) FE-SEM image of templated PY/CM with cylindrical texture after removal of AAO membrane; (b) FL spectra of solution-cast polymer film on glass substrate with the deposition of AAO membrane before (solid line) and after (dash line) solvent annealing; (c) Schematic illustration of the solution-cast polymer film on glass substrate with the deposition of AAO membrane before and after solvent annealing..................................................................................................................100 Figure 4.23 (a) FL spectra of templated PY/CM nanoarrays through solvent-annealing at different annealing times. Inset shows the plot of the intensity of monomer emission (378nm) versus annealing time. (b) SPM tapping-mode height images of nanoporous PS template on spin-coated PY/CM thin film at different solvent-annealing times. The scale of the SPM image is 1μm × 1μm. (c) Schematic illustration of the morphological evolution of pore-filling PY/CM.........................101 Figure 4.24 UV spectra of (a) spin coated 1wt% PY thin film, (b) nanoporous PS template on PY/CM film coated glass slide before solvent-annealing process and (c) templated PY/CM nanoarrays after solvent-annealing process...............................103 Figure 4.25 (a) ATR-FTIR spectra and (b) GI-WAXD of spin-coated PY thin film (dash line), nanoporous PS template on PY/CM thin film (dot line) and templated PY/CM nanoarrays (solid line). Inset of (a) shows the enlarged scale of spectrum from 2900 to 2950 cm-1............................................................................................103 Figure 4.26 Wide-angle X-ray diffraction patterns of drop casting of (a) PY film and (b) CM film..............................................................................................................106 Figure 4.27 Schematic illustration of molecular dispositions for spin-coated PY/CM film before solvent annealing and templated PY/CM nanoarrays...........................106 Figure 4.28 TEM images of templated (a) PM1; (b) PM4; (c) PM10 and (d) PM20 nanoarrays with PTA staining..................................................................................108 Figure 4.29 PL spectra of nanoporous PS templates on spin-coated (a) PM1; (b) PM4; (c) PM10 and (d) PM20 thin films for different solvent-annealing times. Insets show the plot of the intensity of first peak (378 nm, square line) and excimer peak (493nm, circle line) versus different annealing time................................................110 Figure 4.30 2D GI-WAXD patterns of nanoporous PS templates on spin-coated (a) PM4 and (b) PM10 thin films before solvent-annealing times (annealing for 0hr); templated (c) PM4 and (d) PM10 nanoarrays (annealing for 24hr).........................112 Figure 4.31 (a) Normalized PL spectra of templated PY/CM nanoarrays with different mixing ratio. Insets show the plot of the PL integrated area (A) versus different mixing ratio. (b) The plot shows the comparison of the PL integrated area, R=Aafter/Abefore for nanoporous PS template on PY/CM thin film with different mixing ratio before solvent annealing (Abefore) and the formation of templated PY/CM nanoarrays (Aafter)........................................................................................113 Figure 4.32 Polarized PL spectra of nanoporous PS templates on spin-coated (a) PM1; (b) PM4; (c) PM10 and (d) PM20 thin films before solvent-annealing times (annealing for 0hr); templated (e) PM1; (f) PM4; (g) PM10 and (h) PM20 nanoarrays (annealing for 24hr). The spectra were acquired under conditions of vertically polarized excitation with vertically (VV, solid line) or horizontally (VH, dot line) polarized collection. Insets show the plot of DRE versus annealing time…………………………………………………………………………...........115 Figure 4.33 Polarized PL spectra of spin-coated (a), (b)PM1 and (c), (d) PM10 thin films for different solvent-annealing times; (a) and (c) corresponding to the annealing time for 0 hr; (b) and (d) corresponding to the annealing time for 24 hr. The spectra were acquired under conditions of vertically polarized excitation with vertically (VV, solid line) or horizontally (VH, dot line) polarized collection........116 Figure 4.34 GI-FTIR spectra of (a) nanoporous PS templates, (b) spin-coated PY thin film, (c) spin-coated CM thin film and (d) spin-coated PM4 thin film on gold substrate....................................................................................................................117 Figure 4.35 GI-FTIR spectra of nanoporous PS template on different mixing ratio (a) PM1; (b) PM4; (c) PM10 and (d) PM20 thin film before solvent annealing (solid line) and the formation of templated PY/CM nanoarrays after solvent annealing (dash line)...........................................................................................................................119 Figure 4.36 PL decay of different mixing ratio (a) PM1; (b) PM4; (c) PM10 and (d) PM20 thin films on glass substrate with the deposition of nanoporous PS template before (solid line) and after (dash line) solvent annealing.......................................120 Figure 4.37 PL decay of spin-coated PM1 thin film on glass substrate before (solid line) and after (dash line) solvent annealing............................................................121 Figure 4.38 PL decay spectra of spin-coated PM1 thin film on glass substrate with the deposition of nanoporous PS template for different solvent annealing times....121 Figure 4.39 Schematic illustration of molecular orientation for (a) spin-coated 1wt% PY thin film; nanoporous PS templates on spin-coated (b) PM4 and (c) PM20 thin films before solvent annealing; templated (d) PM4 and (e) PM20 nanoarrays.......122 Figure 4.40 TEM images of templated (a) PVE3; (b) PVE7 nanoarrays with PTA staining.....................................................................................................................126 Figure 4.41 PL spectra of spin-coated PVE3 and PVE7 thin films on glass substrate (a), (c) with; (b), (d) without the deposition of nanoporous PS template before (solid line) and after (dot line) solvent annealing for 48hr.................................................126 Figure 4.42 PL spectra of nanoporous PS templates on spin-coated (a) PPV3 and (c) PPV7 thin films for different solvent-annealing times. Insets show the plot of the intensity of first peak (498 nm) versus annealing time. SPM tapping-mode height images of nanoporous PS templates on spin-coated (b) PPV3 and (d) PPV7 thin films for different solvent-annealing times. The scale of the SPM image is 2μm × 2μm...........................................................................................................................128 Figure 4.43 The surface profile along the line in SPM tapping-mode height images of nanoporous PS templates on spin-coated (b) PPV3 and (d) PPV7 thin films for different solvent-annealing times.............................................................................129 Figure 4.44 Schematic illustration of the morphological evolution of pore-filling PVE..........................................................................................................................129 Figure 4.45 Polarized PL spectra of nanoporous PS templates on spin-coated (a), (b) PPV3 and (c), (d) PPV7 thin films for different solvent-annealing times; (a) and (c) corresponding to the annealing time at 0 hr; (b) and (d) corresponding to the annealing time at 48 hr. The spectra were acquired under conditions of vertically polarized excitation with vertically (VV, solid line) or horizontally (VH, dot line) polarized collection. Insets show the plot of DRE versus annealing time................131 Figure 4.46 GI-FTIR spectra of nanoporous PS templates on spin-coated (a) PPV3 and (b) PPV7 thin films for different solvent-annealing times. Insets show the comparison of the R = A3060/A842 of the GI-FTIR absorbance at 3060 cm-1 and 842 cm-1 for different annealing time..............................................................................134 Figure 4.47 PL decay spectra of nanoporous PS template on spin-coated (a) PPV3 and (c) PPV7 thin film before (solid line) and after (dot line) solvent annealing time for 48hr.....................................................................................................................134 Figure 4.48 PL decay spectra of nanoporous PS template on spin-coated (a) PPV3 and (c) PPV7 thin films for different solvent annealing times.................................134 Figure 4.49 Schematic conformation model of GI-FTIR results for spin-coated PVE film with random chain orientation and anisotropic polymer chains along the direction of cylindrical nanopores after solvent annealing......................................135