Scanning Near-Field Optical Lithography and Microscopy of Conjugated Polymer Structures
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Scanning Near-Field Optical Lithography and Microscopy of Conjugated Polymer Structures Oliver Fenwick University College London 2007 i A dissertation submitted for the degree of Doctor of Philosophy UMI Number: U592766 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI U592766 Published by ProQuest LLC 2013. Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 I would like to thank everyone I’ve worked with during the course of this degree. It’s been a very enjoyable experience despite the darkness in the SNOM lab! In particular I would like to thank Andy, Lisa, Antonio and Vlad for helping to get things going in the early days, and of those who I worked with later on I owe a lot to Dan, Gianluca, Soumaya and Laurent. Of course, the most thanks goes to my supervisor, Franco, who has provided knowledge, ideas and equipment through all the stages of the degree and has found numerous excuses to send me to Italy (!). Financial support was from EPSRC (with a top-up from Mum and Dad during the write-up period). Finally, Jennie has been very patient with me and the typos in early drafts of this thesis: an excellent proof reader and an even better girlfriend! I, Oliver Fenwick, confirm that the work presented in this thesis is my own. Where information has been derived from other sources, I confirm that this has been indicated in the thesis. Abstract This thesis is concerned with the use of the scanning near-field optical microscope (SNOM) to pattern and image conjugated polymer structures. The SNOM is one of just a few optical instruments which are capable of breaking the diffraction limit which limits conventional microscopes to a resolution of approximately half a wavelength. It does so by directing light onto a sub-wavelength aperture at the apex of a probe, establishing a local evanescent field of subwavelength dimensions around the aperture. Conjugated polymers on the other hand are an interesting class of materials which have semiconducting properties and a rich photophysics making them suitable for use in novel light-emitting diodes, transistors and solar cells. I demonstrate direct patterning of several conjugated polymers using the SNOM with a resolution extending below 100 nm and attempt to explain the resolution of the lithography through simulations using the Bethe-Bouwkamp model of the field surrounding a sub-wavelength aperture. In particular the modelling focuses on the role of the film thickness and reflections from the substrate. Further experiments demonstrate that thermal effects which can be caused by heating of the SNOM probe do not play a role in lithography with the SNOM in this case. However, I demonstrate the use of a scanning thermal microscope to do a novel and purely thermal lithography on one of the same conjugated polymers. Resolutions of 120 nm are demonstrated, and finite element analysis is used to show that significant improvements in resolution should be possible by optimisation of the probe and the polymer film. In addition, I present simulations of imaging artefacts caused by topography on samples under SNOM investigation, and use the same model to look at the potential of the SNOM to obtain information about sub-surface objects. SNOM images are presented of blends and supramolecular fibres of conjugated polymers. 3 Contents 1. Overview........................................................................................................................................ 11 2. Exploiting the optical near-field..............................................................................................13 2.1 Implementations of near-field microscopy ........................................................................19 2.1.1 Scanning probe microscopy ................................................................................................ 20 2.1.2 Near-field probe design and manufacture ........................................................................... 21 2.1.3 Shear-force feedback ........................................................................................................... 23 2.1.4 Implementations of SNOM and recent developments .........................................................25 2.2 Theoretical description of the near-field ............................................................................28 2.2.1 The Bethe-Bouwkamp model of the near-field from a circular aperture ............................. 28 2.2.2 Other models of the near-field ............................................................................................ 30 3. SNOM apparatus specific to this thesis............................................................................... 32 3.1 SNOM hardware ...................................................................................................................32 3.2 Probes ..................................................................................................................................... 36 4. Overview of conjugated polymers and their devices .........................................................38 4.1 Optical Properties of conjugated polymers ........................................................................ 40 4.2 Optoelectronic conjugated polymer devices ......................................................................45 4.2.1. Polymer light-emitting diodes .............................................................................................. 45 4.2.2. Photovoltaics ........................................................................................................................ 47 4.2.3. Bilayer and blended devices ................................................................................................ 48 5. Scanning near-field optical lithography (SNOL) of conjugated polymers.................51 5.1 Introduction to scanning near-field optical lithography (SNOL) ...................................51 5.1.1. Achievable resolution of SNOL .......................................................................................... 52 5.1.2. Aspect ratio of structures produced by SNOL .................................................................... 54 5.1.3. Apertured vs. Apertureless SNOL ....................................................................................... 55 5.1.4. Patterning of functional materials by SNOL ....................................................................... 56 5.2 Scanning near-field optical lithography of conjugated polymers ..................................58 5.2.1. SNOL of poly(p-phenylene vinylene) .................................................................................58 5.2.2. SNOL of r-F80x and r-BTOx ..............................................................................................61 5.3 Modelling the Resolution of SNOL .................................................................................. 67 5.3.1 Model of a lithographic point ..............................................................................................67 5.3.2 Role of substrate reflections in near-field lithography of thin films ....................................68 5.3.3 Achieving maximum resolution with SNOL ...................................................................... 76 5.4 Probe heating effects during SNOL ................................................................................... 77 5.4.1. Indirect measurement of sample heating in SNOM by thermochromism in PPV ................78 5.4.2. Shape-dependent thermal expansion effects in apertured SNOM probes .............................83 6. Modelling the near-field for imaging ....................................................................................92 6.1 Simulation of artifacts in SNOM images ...........................................................................92 6.2 Investigation of buried structures using the SNOM .......................................................100 6.2.1 Imaging of slanted heterojunctions ....................................................................................100 6.2.2 Imaging of buried objects .................................................................................................. 106 7 Lithography of a conjugated polymer with a microthermal probe ............................ 109 7.1 Background and motivations .............................................................................................109 7.2 System overview ..................................................................................................................I l l 4 7.3 Experimental results............................................................................................................112 7.3.1 Effect of exposure time ....................................................................................................... 113 7.3.2 Thermomechanical effects ..................................................................................................117 7.4 Modelling the temperature