WWW.DISSERTATION.XLIBX.INFO
FREE ELECTRONIC LIBRARY - Dissertations, online materials
 
<< HOME
CONTACTS



Pages:   || 2 | 3 | 4 | 5 |   ...   | 17 |

«PATTERNING OF CONJUGATED POLYMERS FOR ELECTROCHROMIC DEVICES By AVNI ANIL ARGUN A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF ...»

-- [ Page 1 ] --

PATTERNING OF CONJUGATED POLYMERS FOR ELECTROCHROMIC

DEVICES

By

AVNI ANIL ARGUN

A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL

OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT

OF THE REQUIREMENTS FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

Copyright 2004 by Avni A. Argun To Evrim

ACKNOWLEDGMENTS

As I look back upon the years that have led to this dissertation, I have been fortunate to have been surrounded by the help and influence of numerous exceptional people. First, I sincerely thank my advisor, Professor John R. Reynolds, for his inspiring and patient guidance throughout this enjoyable, yet challenging journey. He has served as a great mentor and friend from whom I have learned plenty. He allowed me to pursue the research that I have completed and kept me on the right track with his deep insight and unique enthusiasm.

I wish to thank my supervisory committee members Professors Kenneth B.

Wagener and David B. Tanner for their guidance and valuable discussions throughout my graduate studies, and Professors Alexander Angerhofer and Elliot P. Douglas for their interests in serving on my committee. I extend my thanks to Professor Alan G.

MacDiarmid and Dr. Nicolas J. Pinto for welcoming me to their lab at the University of Pennsylvania to teach me the line patterning method presented in Chapter 4. I also thank the funding agencies AFOSR (F49620-03-1-0091) and the ARO/MURI (DAAD19-99-1for their financial support and Agfa-Gevaert for donation of EDOT and PEDOT/PSS used in this work.

Several coworkers and friends have had an important role during my graduate studies in Gainesville with their discussions and companionships. Thanks go to Dr.

Pierre-Henri Aubert, Dr. Ali Cirpan, Mathieu Berard, and Melanie Disabb for their ongoing friendship and working closely with me on several of the projects presented in iv this dissertation. I would like to thank Ben Reeves and Christophe Grenier for the synthesis of PXDOTs and their contributions in collecting some of the data presented in Chapter 6. Other members of the Reynolds Group who deserve acknowledgement include Dr. Mohamed Bouguettaya, Dr. Said Sadki, Dr. Irina Schwendeman, Dr. Gursel Sonmez, Barry Thompson, and Nisha Ananthakrishnan for being helpful when I needed it. I also thank Maria Nikolou, my collaborator from Dr. Tanner’s Group in Physics, for enjoyable discussions. My time here would not have been the same without the social diversions provided by all my friends in Gainesville. I am particularly thankful to Enes Calik and Omer Ayyer for their continuous friendship and Sertac Ozcan for his pool parties.

For their contributions to my interest in polymer science, I thank my undergraduate advisor Prof. Şefik Süzer at Bilkent University and Prof. Levent Toppare at Middle East Technical University. They taught me valuable life lessons and prepared me well for graduate school. I also thank Emrah Ozensoy who has been my best friend during undergraduate years.

I thank my parents Ayşe and Hasan for allowing me to make my own decisions since I was a little child and preparing me to tackle life wherever it may take me. It is not easy to send a child away from home when he is only 10 years old and expect him to endure the complexities of life. I thank my sister Seher for being a fine example to me since the day she taught me how to read. I also wish to thank Aunt Şadiye for her moral support during my four years in Ankara.

Finally, I give my special thanks to my wife, Evrim, for her true love and support no matter how unbearable I get. She is the source of my inspiration and my ultimate “life improvement.”

–  –  –

ACKNOWLEDGMENTS

LIST OF TABLES

LIST OF FIGURES

ABSTRACT

CHAPTER 1 INTRODUCTION

Conducting Polymers

Electrochromism of Materials

Fundamentals of Electrochromism

Electrochromic Contrast

Coloration Efficiency

Switching Speed

Stability

Optical Memory

The Origin of Electrochromism in Conjugated Polymers

Characterization of Electrochromic Polymers – Methods

Multi-Color Electrochromic Polymers – Color Control

Polymer Electrochromic Devices

Absorption/Transmission ECDs

Reflective ECDs

ECD Applications

General Patterning Methods

Optical Lithography

Electron Beam (e-beam) Lithography

Scanning Probe Lithography

Microcontact Printing (µCP)

Inkjet Printing

Patterning of ECDs

Metal-Vapor Deposition

Line Patterning

Screen Printing

Structure of Dissertation

vi2 EXPERIMENTAL METHODS

Chemicals and Materials

Preparation of Electrodes

Metal Vapor Deposition

Line Patterning

Electroless Metal Plating

All-Polymer Electrodes

Conductivity Measurements

Electrochromic Polymer Deposition

Electrochemical Polymerization

Spray Coating





Device Construction

Electrochemical Methods

Cyclic Voltammetry

Chronocoulometry

Optical Methods

Reflectance Spectroscopy

Spectroelectrochemistry

Single Wavelength Transient Absorption

Colorimetry

3 PATTERNING OF REFLECTIVE ECDS USING SHADOW MASKS..................49

Electrode Patterning

Reflective ECDs from Microporous Gold Electrodes

Device Design and Construction

Spectroelectrochemical Characterization

Electrochromic Switching and Stability

Composite Coloration Efficiency (CCE)

Open Circuit Memory

Energy Consumption

Pixelated Lateral ECDs

Reflective ECDs from Microporous Nickel Electrodes

Back-Side Electrical Contacts for Patterned ECDs

Electrode Preparation

Reflective ECDs

Digit-Display ECD

Conclusions

4 LINE PATTERNING OF METALLIC ELECTRODES FOR LATERAL ECDS....77

Preparation of Patterned Electrodes

Lateral ECDs Using Interdigitated Electrodes (IDEs)

PEDOT-PBEDOT-Cz Lateral ECDs

Lateral ECDs with Varying IDE Spacing

Other Applications of Line Patterning

vii5 ALL ORGANIC ECDS

Line Patterned PEDOT/PSS Electrodes

PEDOT Deposition

PBEDOT-Cz Deposition

Highly Conducting PEDOT/PSS Electrodes

EC Polymers on PEDOT-HAPSS Electrodes

All Organic Electrochromic Devices

Absorptive/transmissive ECDs

Dual-colored ECDs

Conclusions

6 ECDS BASED ON PROCESSABLE DIOXYTHIOPHENE POLYMERS............114

Spray Coated Electrochromic Polymer Films

Optoelectronic Characterization

Thickness Dependence of PProDOT-(EtHx)2 Films

Coloration Efficiency

Electrochromic Devices

Absorptive/Transmissive ECDs

Reflective ECDs

Conclusions

Overall Summary and Perspective

LIST OF REFERENCES

BIOGRAPHICAL SKETCH

–  –  –

1-1 Patterning methods, the highest resolution values achieved from these methods, and their brief description.

3-1 Components used in construction of the reflective electrochromic devices..............53 3-2 Optical reflectivity contrast in the visible (∆%RVIS) and the NIR range (∆%RNIR) for the devices D1-D5..

3-3 Energy consumption data for D1 and D5 type devices

3-4 Metal candidates to be used in reflective ECD applications

5-1 Surface resistance (Rs) and surface resistivity (ρs) values of PEDOT/PSS coated films

5-2 Conductivity enhancement of PEDOT/PSS using additives

5-3 Surface resistivity values of PEDOT-HAPSS

5-4 Coloration efficiency values of a PProDOT-(Me)2/PBEDOT-NMeCz device........110 6-1 Peaks (nm) and Optical Band-gaps (eV) from the UV-Vis spectroscopy of PProDOT derivatives.

6-2 Electrochromic properties of spray cast films

6-3 Optical and electrochemical data for coloration efficiency measurements.............132

–  –  –

1-1 Doping mechanism for PProDOT: (a) Neutral form, (b) Slightly doped radical cation, (c) Fully doped dication

1-2 Spectroelectrochemistry of a PProDOT-(Et)2 film on ITO/Glass at applied potentials between (a) -0.1V and (o) +0.9V vs. Ag/Ag+ with 50 mV increments

1-3 Representative electrochromic polymers. Color swatches are representations of thin films based on measured CIE 1931 Yxy color coordinates.

2-1 Schematic representation of high vacuum metal vapor deposition process.............36 2-2 Line patterning of plastic substrates: (a) PEDOT-PSS electrodes, (b) Electroless gold deposition.

2-3 (a) Surface resistivity measurement of a thin film and (b) Four-probe conductivity measurement setup.

2-4 Potentiodynamic deposition of PProDOT-(Hx)2 on Pt button electrode (Electrode area = 0.02 cm2)

2-5 (a) Schematic representation of an absorption/transmissive type device. (b) A reflective device scheme using porous electrodes

2-6 Chronocoulometry experiment of a PProDOT-(EtHx)2 film on ITO: (a) The potential step, (b) Current and charge curves as a function of time.

2-7 Integrating sphere used for reflective characterization of surface active ECDs......47 3-1 (a) Schematic representation of a reflective type electrochromic device (ECD) using a porous membrane electrode and (b) Cross section of the ECD

3-2 (a) Two gold pixels patterned on a polycarbonate membrane, (b) A 2 x 2 gold pattern, (c) Magnification (80x) of the metallized membrane, and (d) Image of the pattern on the glass backing plate

3-3 (a) Reflectivity contrast (∆%R = %Rneutral - %Roxidized) spectra of D2 PEDOT (A), D3 PProDOT (B), and D5 PProDOT-(Me)2 (C) devices and (b) The two photographs represent (left) the oxidized and (right) the neutral appearance of the active layer...55 x 3-4 Spectroelectrochemistry of a PProDOT-(Me)2 active layer in a D5-inert type reflective device: (a) –0.8V, (b) –0.6V, (c) –0.4V, (d) –0.2V, (e) 0.0V, (f) +0.2V, and (g) +0.4V.

3-5 (a) Temporal change in %R (1540 nm) during electrochromic switching of a D3 type reflective device between –1V and +1V every 1 second and (b) A single transition illustrating the switching time of the same device (-1V to +1V, λ=558 nm).............58 3-6 Long-term switching stability of a D5-inert type device switching between –1V and +1V every 3 seconds.

3-7 Open circuit memory of a D5-inert type device monitored by single-wavelength reflectance spectroscopy. (a) Visible memory at 558 nm and (b) NIR memory at 1540 nm.

3-8 (a) Photographs of EC switching of PEDOT and PBEDOT-B(OR)2 on a 2 x 2 pixel gold/membrane electrode. (b) A 2 x 2 pixels device using the patterned electrodes described above.

3-9 a) Accumulative deposition of PEDOT on a nickel coated microporous polycarbonate membrane (Electrode area = 1.7 cm2). (b) EC switching of a PEDOT device comprising nickel electrodes. Left:

-1.0V, right: +1.0V

3-10 (a) An ion track etched membrane with well-defined pores (left) and a fiber-like porous membrane (right). (b) Reflective optical micrograph of a track-etched membrane. (c) Reflective optical micrograph of a laboratory filter paper...............70 3-11 A reflective type ECD scheme using back-site addressed electrodes. i- Transparent window, ii- PProDOT-(Me)2, iii- Au, iv- Porous membrane, v- Back-side contact, vi- An porous separator, vii- Polymer counter electrode, viii- Au/plastic...............72 3-12 In-situ reflectance spectroelectrochemistry of a PProDOT-(Me)2 ECD. Applied voltages: (a) -1.0V, (b)-0.8V, (c) -0.6V, (d) -0.2V, (e) 0 V, (f) 0.2V, (g) 0.4V, (h)

0.7V, and (i) 1.0V

3-13 Machine-cut masks used to pattern gold on front (a) and back (b) sides of porous membranes. c) Photograph of a 7-pixel electrochromic numeric display device showing the number “5”. Device dimensions: 3cm x 5cm.

4-1 Preparation of line patterned, gold electrodes. (a) Computer generated designs (negative patterns), (b) Photographs of an interdigitated electrode (IDE) and a 3x3 pixels pattern, and (c) Reflective optical micrographs of the electrodes...................79 4-2 Optical micrograph of a 100x magnified line patterned gold substrate to show the resolution limit is down to 30 µm.

4-3 “Color averaging” in lateral type ECDs. (a) Electrochemical deposition of polymer films, (b) EC switching of the resulting ECD.

–  –  –

4-5 Electrochemical switching of a PEDOT/PBEDOT-Cz device with PBEDOT-Cz being the working electrode. (a) Multi-voltage sweep of the device between -0.5V and +1.2V. (b) Chronoamperometry and chronocolulometry of the device..............84 4-6 Negative computer images of IDEs with varying finger widths.

4-7 Multi-sweep CV electropolymerization of (a) PProDOT-(Me)2 and (b) PBEDOT-Cz from their monomer electrolyte solutions onto a 2-lane IDE

4-8 Voltage sweep of 2-lane (black), 4-lane (red), and 6-lane (green) lateral ECDs comprising PProDOT-(Me)2 (working electrode) and PBEDOT-Cz (counter electrode) as the complementary colored polymer pair.

4-9 (a) The %R changes of the 2-lane, 4-lane, and 6-lane devices as a function of time as they are switched from -1.0V to +0.8V. (b) Switching time to reach the 85% of the full contrast as a function of the distance between the anode and the cathode..........88 4-10 EC switching between an absorptive blue state (-1.0V, left) and a reflective state (+0.8V, right).

4-11 EC switching of a cross patterned PEDOT device to yield high contrast (left, -1.0V) and no contrast (right, -0.2V) surfaces.

4-12 EC switching of PEDOT on line patterned, interdigitated ITO/Plastic electrodes..91 5-1 Chemical structure of PEDOT/PSS

5-2 Schematic representation of a PEDOT/PSS (Baytron P) coated, interdigitated plastic electrode.

5-3 %Transmittance of PEDOT/PSS coated substrates vs. air

5-4 Optical microscope pictures of EC PEDOT film on PEDOT/PSS: (a) EC PEDOT film deposited between micro-printed lines, (b) EC PEDOT – PEDOT/PSS interface at the meniscus, (c) Magnification of the interface to show the short



Pages:   || 2 | 3 | 4 | 5 |   ...   | 17 |


Similar works:

«TAINTED PROOFS: STAGING WRITTEN EVIDENCE IN EARLY MODERN DRAMA By Lisa M. Barksdale-Shaw A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of English-Doctor of Philosophy 2015 ABSTRACT TAINTED PROOFS: STAGING WRITTEN EVIDENCE IN EARLY MODERN DRAMA By Lisa M. Barksdale-Shaw Tainted Proofs examines how drama presents stage properties, like letters, contracts, and wills, in the early modern theatre. I argue that the playwrights, William...»

«Instructions for use Development of a novel active targeting system for siRNA delivery to liver sinusoidal endothelial cell in vivo (肝臓類洞内皮細胞へのsiRNA送達を目的とした革新的な能動的標 的化システムの構築) A Dissertation Submitted To The Graduate School of Life Science Hokkaido University In Partial Fulfillment of the Requirements For The Degree of Doctor of Philosophy Laboratory of Innovative Nanomedicine Department of Biomedical and Pharmaceutical...»

«CONSEQUENCES OF APOLIPOPROTEIN E ISOFORM VARIATION: EFFECTS ON HIPPOCAMPUS SYNAPTIC PLASTICITY, LEARNING AND MEMORY IN THE ADULT MOUSE By Kimberly Korwek Dissertation Submitted to the Faculty of the Graduate School of Vanderbilt University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Neuroscience August, 2009 Nashville, Tennessee Approved: Professor Edwin J. Weeber Professor Danny G. Winder Professor Roger J. Colbran Professor Alyssa H. Hasty...»

«EPHEMERAL SPACES, UNDYING DREAMS: SOCIAL JUSTICE STRUGGLES IN CONTEMPORARY PUERTO RICO A Dissertation Presented to the Faculty of the Graduate School of Cornell University in Partial Fufillment of the Requirements for the Degree of Doctor of Philosophy By Melissa Lynn Rosario August 2013 © 2013 Melissa Lynn Rosario ALL RIGHTS RESERVED EPHEMERAL SPACES, UNDYING DREAMS: SOCIAL JUSTICE STRUGGLES IN CONTEMPORARY PUERTO RICO Melissa Lynn Rosario, Ph.D. Cornell University, 2013 The premise of this...»

«COUNTERING MURPHY’S LAW: THE USE OF ANTICIPATION AND IMPROVISATION VIA AN EPISODIC MEMORY IN SUPPORT OF INTELLIGENT ROBOT BEHAVIOR A Dissertation Presented to the Academic Faculty by Yoichiro Endo In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Interactive Computing College of Computing Georgia Institute of Technology December 2008 Copyright © 2008 by Yoichiro Endo COUNTERING MURPHY’S LAW: THE USE OF ANTICIPATION AND IMPROVISATION VIA AN...»

«EXPERIENTIAL LEARNING IN UNDERGRADUATE PHARMACY CURRICULUM: A CASE STUDY OF COOPERATIVE EXPERIENCE OF PHARMACY STUDENTS by Kum Tong Certina Ho A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Curriculum, Teaching and Learning Ontario Institute for Studies in Education University of Toronto © Copyright by Kum Tong Certina Ho (2016) EXPERIENTIAL LEARNING IN UNDERGRADUATE PHARMACY CURRICULUM: A CASE STUDY OF CO-OPERATIVE EXPERIENCE OF...»

«ABSTRACT Title of Dissertation: COMMUNICATION INTERFACE PROXIMITY AND USER ANXIETY: COMPARING DESKTOP, LAPTOP, AND HAND-HELD DEVICES AS MEDIA PLATFORMS FOR EMERGENCY ALERTS Wenjing Xie, Doctor of Philosophy, 2009 Directed By: Professor John E. Newhagen Philip Merrill College of Journalism This study is an experiment investigating the effects of communication interface proximity on college students’ anxiety when they receive the alerts about on-campus crimes via e-mails and text messages. It...»

«FLUID SHEAR STRESS MODULATION OF EMBRYONIC STEM CELL DIFFERENTIATION A Dissertation Presented to The Academic Faculty by Barbara A. Nsiah In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in Bioengineering in the George W. Woodruff School of Mechanical Engineering Georgia Institute of Technology May 2012 FLUID SHEAR STRESS MODULATION OF EMBRYONIC STEM CELL DIFFERENTIATION Approved by: Dr. Todd C. McDevitt, Advisor Dr. Evan A. Zamir School of Biomedical Engineering...»

«Investigations into the Optically Stimulated Luminescence Response of Various Materials by William Geoffrey West A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Nuclear Engineering and Radiological Sciences) in the University of Michigan 2011 Doctoral Committee: Professor Kimberlee J. Kearfott, Chair Professor Rodney C. Ewing Professor Ronald M. Gilgenbach Professor Zhong He Joseph A. Miklos © William Geoffrey West 2011 For Dad ii...»

«Body and Soul in Ancient Philosophy Edited by Dorothea Frede and Burkhard Reis Walter de Gruyter · Berlin · New York Contents Introduction....................................... 1 I. Presocratics Carl Huffman The Pythagorean conception of the soul from Pythagoras to Philolaus.......................................... 21 Christian Schäfer Das Pythagorasfragment des Xenophanes und die Frage nach der Kritik der...»

«ASSESSMENT OF WATER RESOURCES IN A HUMID WATERSHED AND A SEMI-ARID WATERSHED; NECHES RIVER BASIN, TX AND CANADIAN RIVER BASIN, NM A Dissertation by JOONG HYEOK HEO Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Chair of Committee, Rick Giardino Co-Chair of Committee, Jaehyung Yu Committee Members, John Vitek Christopher Mathewson Hongbin Zhan Head of Department, Rick Giardino August 2013 Major...»

«Dissertation for the degree philosophiae doctor (PhD) at the University of Bergen Dissertation date: ACKNOWLEDGEMENTS ABSTRACT LIST OF PUBLICATIONS ABBREVIATIONS 1 INTRODUCTION 1.1 Gliomas 1.1.1 Classification and grading 1.1.2 Incidence and prognosis 1.1.3 Conventional therapies 1.1.4 Challenges associated with the treatment of GBMs 1.2 Anti-angiogenic therapy 1.2.1 Anti-angiogenic compounds 1.2.2 Response to anti-angiogenic therapy and adaptation mechanisms 1.3 Modalities for the imaging of...»





 
<<  HOME   |    CONTACTS
2016 www.dissertation.xlibx.info - Dissertations, online materials

Materials of this site are available for review, all rights belong to their respective owners.
If you do not agree with the fact that your material is placed on this site, please, email us, we will within 1-2 business days delete him.