Multilayer thin films by layer-by-layer (LBL) assembly of functional polyelectrolytes [Elektronische Ressource] : their optical and electrochemical properties / von Kyungsun Choi

Vennesm

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2006
• Nombre de lectures: 55
• Poids de l'ouvrage: 3 Mo

Extrait

Multilayer Thin Films by Layer-by-Layer (LBL) Assembly of
Functional Polyelectrolytes: Their Optical and Electrochemical
Properties.






Dissertation

Zur Erlangung des Grades
“Doktor der Naturwissenschaften”
am Fachbereich Chemie, Pharmazie und Geowissenschaften
der Johannes-Gutenberg-Universität in Mainz








von M.Sc. Kyungsun Choi

geboren in Seoul, Korea

Mainz 2006PUBLICATIONS

[1] “Amphotropic LC Polymers and Their Multilayer Build-up”, K. Choi, R. Mruk, A.
Moussa, A. M. Jonas, R. Zentel, Macromolecules 2005, 38, 9124.
[2] “Electrochemical and Electrochromic Properties of Layer-by-Layer Polymer Films”,
K. Choi, R. Zentel, Polymer Preprints. 2006, 47, 1, 386.
[3] “Multilayer Thin Films by Layer-by-Layer Assembly of Hole and Electron Transport
Polyelectrolytes: Their Optical and Electrochemical Properties.”, K. Choi, R. Zentel,
Macromol. Chem. Phys. 2006, 207, 1870.
[4] "High Contrast Ratio and Rapid Switching Organic Polymeric Electrochromic thin
films Based on Triarylamine derivatives from Layer-by-Layer Assembly”. K. Choi, S.
Yoo, Y. E. Sung, R. Zentel, Chem. Mater. 2006, accepted.
[5] “Vacuum-deposited Triarylamine Polymer Thin-Film and Its Structure and Electronic
Properties as Hole Transporting Layer”. K. Choi, J. Kwak, C. Lee, H. Kim, K. Char,
D. Kim, R. Zentel, Chemical Vapor Deposition. 2006, submitted.

POSTERS

[1] "Electrochemical and electrochromic properties of Layer-by-Layer polymer films" K.
Choi, R. Zentel, 231st ACS National Meeting, Atlanta, oral presentation session,
March 2006, U. S. A.
[2] “Multilayer Thin Films by Layer-by-Layer Assembly of Hole and Electron Transport
Polyelectrolytes: Their Optical and Electrochemical Properties” K. Choi, R. Zentel,
September 2006, CDCh, Mainz, Germnay.
I TABLE OF CONTENTS

1. Introduction………………………………………………………………1
1.1. Layer-by-Layer (LBL) Assembly ...................................................................... 2
1.1.1. Basic Mechanism of LBL Assembly……………………………………2
1.1.2. Multilayer Structures ..............................................................................6
1.1.3. Various LBL Assemblies ........................................................................8
1.2. Materials for LBL Assembly ...........................................................................11
1.3. Functional LBL Assemblies with Electroactive Properties………………...15
1.3.1. Electrochromic Devices (ECDs) ………………………………………15
1.3.2. Light emitting Devices (LEDs) ………………………………………..18
1.4. References.......................................................................................................... 23

2. Aim of the Work ………………………………………………………..27

3. Amphotropic LC Polymers and Their Multilayer Build-up…………..31
3.1. Introduction....................................................................................................... 31
3.2. Results and Discussion...................................................................................... 33
3.3. Conclusions........................................................................................................ 46
3.4. Experimental ..................................................................................................... 48
3.5. References.......................................................................................................... 55

4. Multilayer Thin Films by Layer-by-Layer Assembly of Hole and
Electron Transport Polyelectrolytes: Their Optical and Electrochemical
Properties...................................................................................................... 58
II 4.1. Introduction....................................................................................................... 58
4.2. Results and Discussion...................................................................................... 61
4.3. Conclusions........................................................................................................ 69
4.4. Experimental ..................................................................................................... 70
4.5. References.......................................................................................................... 77

5. High Contrast Ratio and Rapid Switching Organic Polymeric
Electrochromic Thin Films based on Triarylamine derivatives from
Layer-by-Layer Assembly........................................................................... 79
5.1. Introduction....................................................................................................... 79
5.2. Results and Discussion...................................................................................... 81
5.3. Conclusions........................................................................................................ 87
5.4. Experimental ..................................................................................................... 88
5.5. References.......................................................................................................... 91

6. Vacuum-deposited Triarylamine Thin Film and Its Structure and
Electronic Properties. .................................................................................. 94
6.1. Introduction....................................................................................................... 94
6.2. Results and Discussion...................................................................................... 95
6.3. Conclusions...................................................................................................... 103
6.4. Experimental ................................................................................................... 104
6.5. References........................................................................................................ 106

7. Summary and Conclusions ................................................................... 108

III 8. Methods and Instrumentation.............................................................. 110
8.1. Surface Plasmon Resonance Spectroscopy (SPR)........................................ 110
8.2. Atomic Force Microscopy (AFM).................................................................. 114
8.3. Cyclic Voltammetry (CV)............................................................................... 117
8.4. References........................................................................................................ 120

9. Appendix................................................................................................. 121
9. 1. List of Figures 121
9. 2. List of Schemes............................................................................................... 125
9. 3. List of Tables .................................................................................................. 126
9. 4. List of Abbreviations ..................................................................................... 127




IV Introduction

1. Introduction

Nanoscience is the world of atoms, molecules, macromolecules, quantum dots, and
macromolecular assemblies and it aims at manipulating atoms, molecules and nanosize
1particles in a precise and controlled manner. It is dominated by surface effects such as van
der Waals force attraction, hydrogen bonding, electronic charge, ionic bonding, covalent
bonding, hydrophobicity, hydrophilicity, quantum mechanical tunneling and the virtual
exclusion of macro-scale effects such as turbulence and inertia. For example, the vastly
increased ratio of surface area to volume opens new possibilities in surface-based science,
such as catalysis. The fascination with nanotechnology stems from these unique quantum and
surface phenomena that matter exhibits at the nano-scale, making possible novel applications
and interesting materials.

One promise of nanoscience is improvement in thin-film structures with increased surface
area of a material. Nano-scale control of the structure of organic/polymeric materials is a
prerequisite to the fabrication of sophisticated functional devices. In this dissertation, so-
called layer-by-layer (LBL) assembly technique is particularly used as simple system wherein
nano-scale control of the structure in one direction is easily attainable. The ionic self-
assembly technique, introduced by Decher in 1991 (G. Decher, Macromol. Chem. Macormol.
Symp., 1991, 46, 321-327) provides an elegant way of controlling the composition of the
resulting assemblies and the thickness of an individual layer on the nanometer scale. This
method can easily be adapted for automated fabrication, and is applicable to any substrate
shape. The thickness of a single polyelectrolytes layer is of the order of several Angstroms
and, therefore, the total film thickness can be precisely controlled by the number of adsorbed
layers. Large varieties of charged materials, including almost all kinds of polyions, dyes,
organic/inorganic particles, proteins, viruses, and other biosystems have been incorporated
into multilayer assemblies using this technique. These thin film assemblies ha