From c2a08c2b580ddf5002012d6149b9ff7a4e20a00e Mon Sep 17 00:00:00 2001 From: Blaise Thompson Date: Mon, 26 Feb 2018 10:27:18 -0600 Subject: 2018-02-26 10:27 --- PEDOT:PSS/beam waist.png | Bin 0 -> 82375 bytes PEDOT:PSS/chapter.tex | 170 ++++++++++++++++++++++++++++++++- PEDOT:PSS/compare 2D.png | Bin 0 -> 1440621 bytes PEDOT:PSS/compare slices.png | Bin 0 -> 372559 bytes PEDOT:PSS/compare.png | Bin 0 -> 484738 bytes PEDOT:PSS/delay space.png | Bin 0 -> 117602 bytes PEDOT:PSS/excitation pulse spectra.png | Bin 0 -> 112000 bytes PEDOT:PSS/linear.png | Bin 0 -> 178770 bytes PEDOT:PSS/main.png | Bin 0 -> 445523 bytes PEDOT:PSS/mask.png | Bin 0 -> 143220 bytes PEDOT:PSS/overtraces.png | Bin 0 -> 368434 bytes PEDOT:PSS/peak shift.png | Bin 0 -> 187305 bytes PEDOT:PSS/processed.png | Bin 0 -> 1960170 bytes PEDOT:PSS/raw.png | Bin 0 -> 710687 bytes PEDOT:PSS/substrate.png | Bin 0 -> 384158 bytes PEDOT:PSS/traces.png | Bin 0 -> 804127 bytes bibliography.bib | 15 +++ dissertation.pdf | Bin 30175819 -> 3303728 bytes dissertation.syg | 3 - dissertation.tex | 28 +++--- introduction/chapter.tex | 37 +++++++ 21 files changed, 235 insertions(+), 18 deletions(-) create mode 100644 PEDOT:PSS/beam waist.png create mode 100644 PEDOT:PSS/compare 2D.png create mode 100644 PEDOT:PSS/compare slices.png create mode 100644 PEDOT:PSS/compare.png create mode 100644 PEDOT:PSS/delay space.png create mode 100644 PEDOT:PSS/excitation pulse spectra.png create mode 100644 PEDOT:PSS/linear.png create mode 100644 PEDOT:PSS/main.png create mode 100644 PEDOT:PSS/mask.png create mode 100644 PEDOT:PSS/overtraces.png create mode 100644 PEDOT:PSS/peak shift.png create mode 100644 PEDOT:PSS/processed.png create mode 100644 PEDOT:PSS/raw.png create mode 100644 PEDOT:PSS/substrate.png create mode 100644 PEDOT:PSS/traces.png diff --git a/PEDOT:PSS/beam waist.png b/PEDOT:PSS/beam waist.png new file mode 100644 index 0000000..1e99afc Binary files /dev/null and b/PEDOT:PSS/beam waist.png differ diff --git a/PEDOT:PSS/chapter.tex b/PEDOT:PSS/chapter.tex index c7dc807..9138972 100644 --- a/PEDOT:PSS/chapter.tex +++ b/PEDOT:PSS/chapter.tex @@ -1 +1,169 @@ -\chapter{PEDOT:PSS} \ No newline at end of file +\chapter{PEDOT:PSS} + +\section{Introduction} + +Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) is a transparent, electrically +conductive (up to 4380 S cm$^{-1}$ \cite{KimNara2013a}) polymer. % +It has found widespread use as a flexible, cheap alternative to inorganic transparent electrodes +such as indium tin oxide. % + +As a polymer, PEDOT:PSS implicitly contains a large amount of structural inhomogeneity. % +On top of this, PEDOT:PSS is a two component material, composed of PEDOT (low molecular weight, +p-doped, highly conductive) and PSS (high molecular-weight, insulating, stabilizing). % +These two components segment into domains of conductive and non-conductive material, leading to +even more structural inhomogeneity. % +Nonlinear spectroscopy may be able to shed light on the microscopic environment of electronic +states within PEDOT:PSS. % + +\section{Background} + +Complex microstructure: +\begin{enumerate} + \item PEDOT oligomers (6---18-mers) + \item these oligomers $\pi$-stack to form small nanocrystalites, 3 to 14 oligomers for pristine + films to as many as 13---14 oligomers for more conductive solvent treated films + \item nanocrystallites then arrange into globular conductive particles in a pancakge-like shape + \item these particles themselves are then linked via PSS-rich domains and assembled into + nanofibril geometry akin to a string of pearls + \item nanofibrils interweave to form thin films, with PSS capping layer at surface +\end{enumerate} + +Prior spectroscopy (absorption anisotropy, X-ray scattering, condutivity). % + +% TODO: absorption spectrum of thin film + +Broad in the infrared due to midgap states created during doping from charge-induced lattice +relaxations. % +These electronic perturbations arise from injected holes producing a quinoidal distortion spread +over 4-5 monomers of the CP aromatic backbone, collectively called a polaron. % +Energetically favorable to be spin-silent bipolaron. % + +\section{Methods} + +PEDOT:PSS (Orgacon Dry, Sigma Aldrich) was dropcast onto a glass microscope slide at 1 mg/mL at a +tilt to ensure homogeneous film formation. % +The sample was heated at 100 $^\circ$C for $\sim$15 min to evaporate water. % + +An ultrafast oscillator (Spectra-Physics Tsunami) was used to prepare $\sim$35 fs seed pulses. % +These were amplified (Spectra-Physics Spitfire Pro XP, 1 kHz), split, and converted into 1300 nm 40 +fs pulses using two separate optical parametric amplifiers (Light Conversion TOPAS-C): ``OPA1'' and +``OPA2''. % +Pulses from OPA2 were split again, for a total of three excitation pulses: $\omega_1$, $\omega_2$ +and $\omega_{2^\prime}$. % +These were passed through motorized (Newport MFA-CC) retroreflectors to control their relative +arrival time (``delay'') at the sample: $\tau_{21} = \tau_2 - \tau_1$ and $\tau_{22^\prime} = +\tau_2 - \tau_{2^\prime}$. The three excitation pulses were focused into the sample in a $1^\circ$ +right-angle isoceles triange, as in the BOXCARS configuration. \cite{EckbrethAlanC1978a} % +Each excitation beam was 67 nJ focused into a 375 $\mathsf{\mu m}$ symmetric Gaussian mode for an +intensity of 67 $\mathsf{\mu J / cm^2}$. % +A new beam, emitted coherently from the sample, was isolated with apertures and passed into a +monochromator (HORIBA Jobin Yvon MicroHR, 140 mm focal length) with a visible grating (500 nm blaze +300 groves per mm). % +The monochromator was set to pass all colors (0 nm, 250 $\mathsf{\mu m}$ slits) to keep the +measurement impulsive. % +Signal was detected using an InSb photodiode (Teledyne Judson J10D-M204-R01M-3C-SP28). % +Four wave mixing was isolated from excitation scatter using dual chopping and digital signal +processing. % + +\section{Transmittance and reflectance} + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/linear"} + \caption[PEDOT:PSS transmission and reflectance spectra.]{ + Thin film spectra. + Transmission, reflectance, and extinction spectrum of the thin film used in this work. % + Extinction is $\log_{10}{\mathsf{(transmission)}}$. % + } + \label{fig:PEDOTPSS_linear} +\end{figure} +\clearpage} + +\autoref{fig:PEDOTPSS_linear} shows the transmission, reflectance, and extinction spectrum of the +thin film used in this work. % + +\section{Three-pulse echo spectroscopy} + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/mask"} + \caption[PEDOT:PSS 3PE phase matching mask.]{ + Phase matching mask used in this experiment. + Each successive ring subtends 1 degree, such that the excitation pulses are each angled one + degree relative to the mask center. + The two stars mark the two output poyntings detected in this work. + } + \label{fig:PEDOTPSS_mask} +\end{figure} +\clearpage} + +Two dimensional $\tau_{21}, \tau_{22^\prime}$ scans were taken for two phase matching +configurations: (1) $k_{\mathsf{out}} = k_1 - k_2 + k_{2^\prime}$ (3PE) and (2) $k_{\mathsf{out}} = +k_1 + k_2 - k_{2^\prime}$ (3PE*). % +The rephasing and nonrephasing pathways exchange their time dependance between these two +configurations. % +Comparing both pathways, rephasing-induced peak shifts can be extracted as in 3PE. [CITE] % +All data was modeled using numerical integration of the Liouville-von Numann equation. % + +Continuously variable ND filters (THORLABS NDC-100C-4M, THORLABS NDL-10C-4) were used to ensure +that all three excitation pulse powers were equal within measurement error. % + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/raw"} + \caption[PEDOT:PSS 3PE raw data.]{ + CAPTION TODO + } + \label{fig:PEDOTPSS_raw} +\end{figure} +\clearpage} + + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/processed"} + \caption[PEDOT:PSS 3PE processed data.]{ + CAPTION TODO + } + \label{fig:PEDOTPSS_processed} +\end{figure} +\clearpage} + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/delay_space"} + \caption[PEDOT:PSS 3PE delay space.]{ + CAPTION TODO + } + \label{fig:PEDOTPSS_delay_space} +\end{figure} +\clearpage} + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/traces"} + \caption[PEDOT:PSS 3PE traces.]{ + CAPTION TODO + } + \label{fig:PEDOTPSS_traces} +\end{figure} +\clearpage} + +\afterpage{ +\begin{figure} + \centering + \includegraphics[width=0.5\linewidth]{"PEDOT:PSS/overtraces"} + \caption[PEDOT:PSS 3PE traces.]{ + CAPTION TODO + } + \label{fig:PEDOTPSS_overtraces} +\end{figure} +\clearpage} + +\section{Frequency-domain transient grating spectroscopy} \ No newline at end of file diff --git a/PEDOT:PSS/compare 2D.png b/PEDOT:PSS/compare 2D.png new file mode 100644 index 0000000..e42cb42 Binary files /dev/null and b/PEDOT:PSS/compare 2D.png differ diff --git a/PEDOT:PSS/compare slices.png b/PEDOT:PSS/compare slices.png new file mode 100644 index 0000000..8433b81 Binary files /dev/null and b/PEDOT:PSS/compare slices.png differ diff --git a/PEDOT:PSS/compare.png b/PEDOT:PSS/compare.png new file mode 100644 index 0000000..2cfd095 Binary files /dev/null and b/PEDOT:PSS/compare.png differ diff --git a/PEDOT:PSS/delay space.png b/PEDOT:PSS/delay space.png new file mode 100644 index 0000000..1fed3f6 Binary files /dev/null and b/PEDOT:PSS/delay space.png differ diff --git a/PEDOT:PSS/excitation pulse spectra.png b/PEDOT:PSS/excitation pulse spectra.png new file mode 100644 index 0000000..01d2426 Binary files /dev/null and b/PEDOT:PSS/excitation pulse spectra.png differ diff --git a/PEDOT:PSS/linear.png b/PEDOT:PSS/linear.png new file mode 100644 index 0000000..7c48bed Binary files /dev/null and b/PEDOT:PSS/linear.png differ diff --git a/PEDOT:PSS/main.png b/PEDOT:PSS/main.png new file mode 100644 index 0000000..e1f10d8 Binary files /dev/null and b/PEDOT:PSS/main.png differ diff --git a/PEDOT:PSS/mask.png b/PEDOT:PSS/mask.png new file mode 100644 index 0000000..418e928 Binary files /dev/null and b/PEDOT:PSS/mask.png differ diff --git a/PEDOT:PSS/overtraces.png b/PEDOT:PSS/overtraces.png new file mode 100644 index 0000000..767517c Binary files /dev/null and b/PEDOT:PSS/overtraces.png differ diff --git a/PEDOT:PSS/peak shift.png b/PEDOT:PSS/peak shift.png new file mode 100644 index 0000000..42e7b43 Binary files /dev/null and b/PEDOT:PSS/peak shift.png differ diff --git a/PEDOT:PSS/processed.png b/PEDOT:PSS/processed.png new file mode 100644 index 0000000..32b210c Binary files /dev/null and b/PEDOT:PSS/processed.png differ diff --git a/PEDOT:PSS/raw.png b/PEDOT:PSS/raw.png new file mode 100644 index 0000000..58cef4a Binary files /dev/null and b/PEDOT:PSS/raw.png differ diff --git a/PEDOT:PSS/substrate.png b/PEDOT:PSS/substrate.png new file mode 100644 index 0000000..2a5fe49 Binary files /dev/null and b/PEDOT:PSS/substrate.png differ diff --git a/PEDOT:PSS/traces.png b/PEDOT:PSS/traces.png new file mode 100644 index 0000000..7ffc5d0 Binary files /dev/null and b/PEDOT:PSS/traces.png differ diff --git a/bibliography.bib b/bibliography.bib index 6b2a454..66d59c9 100644 --- a/bibliography.bib +++ b/bibliography.bib @@ -271,6 +271,21 @@ month = {jan}, } +@article{KimNara2013a, + author = {Nara Kim and Seyoung Kee and Seoung Ho Lee and Byoung Hoon Lee and Yung Ho Kahng + and Yong-Ryun Jo and Bong-Joong Kim and Kwanghee Lee}, + title = {Highly Conductive {PEDOT}:{PSS} Nanofibrils Induced by Solution-Processed + Crystallization}, + journal = {Advanced Materials}, + volume = 26, + number = 14, + pages = {2268--2272}, + year = 2013, + doi = {10.1002/adma.201304611}, + month = {dec}, + publisher = {Wiley-Blackwell}, +} + @article{KohlerDanielDavid2014a, author = {Daniel D. Kohler and Stephen B. Block and Schuyler Kain and Andrei V. Pakoulev and John C. Wright}, diff --git a/dissertation.pdf b/dissertation.pdf index 5a07659..7cfeb9a 100644 Binary files a/dissertation.pdf and b/dissertation.pdf differ diff --git a/dissertation.syg b/dissertation.syg index 7b1944a..e69de29 100644 --- a/dissertation.syg +++ b/dissertation.syg @@ -1,3 +0,0 @@ -\glossaryentry{\ensuremath {N}?\glossentry{N}|setentrycounter[]{page}\glsnumberformat}{8} -\glossaryentry{\ensuremath {N}?\glossentry{N}|setentrycounter[]{page}\glsnumberformat}{8} -\glossaryentry{\ensuremath {\omega }?\glossentry{omega}|setentrycounter[]{page}\glsnumberformat}{74} diff --git a/dissertation.tex b/dissertation.tex index 3bf6bb6..4bc47a2 100644 --- a/dissertation.tex +++ b/dissertation.tex @@ -192,30 +192,30 @@ This dissertation is approved by the following members of the Final Oral Committ \include{introduction/chapter} \part{Background} -\include{spectroscopy/chapter} -\include{materials/chapter} -\include{mixed_domain/chapter} +%\include{spectroscopy/chapter} +%\include{materials/chapter} +%\include{mixed_domain/chapter} \part{Instrumental Development} -\include{software/chapter} -\include{instrument/chapter} +%\include{software/chapter} +%\include{instrument/chapter} \part{Applications} -\include{PbSe/chapter} -\include{MX2/chapter} +%\include{PbSe/chapter} +%\include{MX2/chapter} \include{PEDOT:PSS/chapter} -\include{pyrite/chapter} -\include{BiVO4/chapter} +%\include{pyrite/chapter} +%\include{BiVO4/chapter} % appendix ----------------------------------------------------------------------------------------- \part{Appendix} \begin{appendix} -\include{public/chapter} -\include{procedures/chapter} -\include{hardware/chapter} -\include{errata/chapter} -\include{colophon/chapter} +%\include{public/chapter} +%\include{procedures/chapter} +%\include{hardware/chapter} +%\include{errata/chapter} +%\include{colophon/chapter} \end{appendix} % post -------------------------------------------------------------------------------------------- diff --git a/introduction/chapter.tex b/introduction/chapter.tex index 3424a35..81a6b97 100644 --- a/introduction/chapter.tex +++ b/introduction/chapter.tex @@ -8,5 +8,42 @@ \section{The CMDS Instrument} +From an instrumental perspective, MR-CMDS is a problem of calibration and coordination. % +Within the Wright Group, each of our two main instruments are composed of roughly ten actively +moving component hardwares. % +Many of these components are purchased directly from vendors such as SpectraPhysics, National +Instruments, Horiba, Thorlabs, and Newport. % +Others are created or heavily modified by graduate students. % +The Wright Group has always maintained custom acquisition software packages which control the +complex, many-stepped dance that these components must perform to acquire MR-CMDS spectra. % + \section{Scientific Software} +When I joined the Wright Group, I saw that acquisition software was a real barrier to experimental +progress and flexibility. % +Graduate students had ideas for instrumental enhancements that were infeasible because of the +challenge of incorporating the new components into the existing software ecosystem. % +At the same time, students were spending much of their time in lab repeatedly calibrating optical +parametric amplifiers by hand, a process that sometimes took days. % +I chose to spend a significant portion of my graduate career focusing on solving these problems +through software development. % +At first, I focused on improving the existing LabVIEW code. % +Eventually, I developed a vision for a deeply modular acquisition software that could not be +practically created with LabVIEW. % +Using Python and Qt, I created a brand new acquisition software PyCMDS: built from the ground up to +fundamentally solve historical challenges in the Group. % +PyCMDS offers a modular hardware model that can ``re-configure'' itself to flexibly control a +variety of component hardware configurations. % +This has enabled graduate students to add and remove hardware whenever necessary, without worrying +about a heavy additional programming burden. % +PyCMDS is now used to drive both MR-CMDS instruments in the Group, allowing for easy sharing of +component hardware and lessening the total amount of software that the Group needs to maintain. % +Besides being more flexible, PyCMDS solves a number of other problems. % +It offers fully automated strategies for calibrating component hardwares, making calibration less +arduous and more reproducible. % +It offers more fine-grained control of data acquisition and timing, enabling more complex +algorithms to quickly acquire artifact-free results. % +In conjunction with other algorithmic and hardware improvements that I have made, PyCMDS has +decreased acquisition times by up to two orders of magnitude. % +A companion software, WrightTools (which I also created), solves some of the processing and +representation challenges of multidimensional data. % \ No newline at end of file -- cgit v1.2.3