From c2a08c2b580ddf5002012d6149b9ff7a4e20a00e Mon Sep 17 00:00:00 2001
From: Blaise Thompson <blaise@untzag.com>
Date: Mon, 26 Feb 2018 10:27:18 -0600
Subject: 2018-02-26 10:27

---
 PEDOT:PSS/chapter.tex | 170 +++++++++++++++++++++++++++++++++++++++++++++++++-
 1 file changed, 169 insertions(+), 1 deletion(-)

(limited to 'PEDOT:PSS/chapter.tex')

diff --git a/PEDOT:PSS/chapter.tex b/PEDOT:PSS/chapter.tex
index c7dc807..9138972 100644
--- a/PEDOT:PSS/chapter.tex
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@@ -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
-- 
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