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%\title{\bf Characterisation of nanostructured thin films}
%\author{Sam Moore\\ School of Physics, University of Western Australia}
%\date{April 2012}
%\maketitle

\begin{center}
        B.Sc. (Hons) Physics Project \par
        {\bf \Large Thesis} \par
        Samuel Moore \\
        School of Physics, University of Western Australia \\
        April 2012
\end{center}
\section*{Characterisation of Nanostructured Thin Films}
{\bf \emph{Keywords:}} surface plasmons, nanostructures, spectroscopy, metallic-blacks \\
{\bf \emph{Supervisers:}} W/Prof. James Williams (UWA), Prof. Sergey Samarin (UWA) \\


%\tableofcontents

\section*{Acknowledgements}
\begin{itemize}
        \item Sergey Samarin
        \item Jim Williams
        \item Paul Guagliardo
        \item Nikita Kostylev
        \item Workshop (for producing electron gun mount?)
        \item Peter Hammond (?)
\end{itemize}

\section{Introduction}
\begin{itemize}
        \item Waffle about motivation for the project
        \begin{itemize}
                \item Metal-Black films may have application for ... something.
                \begin{itemize}
                        \item Radiometer vanes, IR detectors
                        \item Number of applications where high absorbance into IR is required
                        \item These have all been studied before though. 
                \end{itemize}
                \item The electron spectra of metal-blacks have not yet been examined.
                \item Remarkable difference between Metal-Black films (bad vacuum) and normal metal films (UHV)
                \begin{itemize}
                        \item No (detailed/satisfactory) explanation (that I can find...) for difference
                \end{itemize}
                \item Talk about plasmonic based computing? Moore's law? Applications to thin film solar cells?

        \end{itemize}
        \item Specific aims of project
        \begin{enumerate}
                \item Surface density of states / band structure of Black-Au films using TCS (The main aim)
                \item Identification of plasmonic effects in Black-Au films (?) (If they even exist!)
                \begin{itemize}
                        \item Identify plasmonic effects in Au and Ag films with Ellipsometry (this is fairly simple to do)
                \end{itemize}
                \item Combination of Ellipsometry and TCS to characterise thin films (not just Black-Au)
                \begin{itemize}
                        \item Ie: How can one technique be used to support the other?
                \end{itemize}
        \end{enumerate}
        \item Structure of thesis
\end{itemize}

\section{Overview of Theory}
Summarise the literature, refer to past research etc

\subsection{Electron Spectra of a Surface}
\begin{itemize}
        \item Description of the near surface region
        \begin{itemize}
                \item All real solids occupy finite volumes in space.
                \item The surface of a solid is important because interactions between the solid and its surroundings occur in the near surface region.
                \item Characterised physically by:
                \begin{itemize}
                        \item Termination of periodic crystal lattice
                        \item Violation of geometric order
                        \item Distortion of interatomic distances and hence interaction forces
                        \item There is a transition ``near surface'' region between bulk and surface properties, roughly 5 atomic distances. 
                \end{itemize}
                \item Potential seen by an electron at a surface can differ greatly from the bulk
                \item $\implies$ the electron spectra of the near surface region differs from the bulk spectra
                \item Simplest case: Step potential at surface.
                
        \end{itemize}

        \item The Electron Spectra
        \begin{itemize}
                \item Electron Spectra describes the energy eigenstates for an electron in a Bulk or Surface potential
                \item Characterised by 
                \begin{enumerate}
                        \item Energy dispersion $E(\vect{k})$
                        \begin{itemize}
                                \item Dependence of Energy on electron wave vector
                                \item Obtained theoretically by solving Scrhrodinger's Equation
                                \item For a free electron gas, $E = \frac{\hbar^2 k^2}{2m}$
                                \item Periodic potential in bulk solid leads to band gap structure of $E(\vect{k})$
                                \item Periodic potential $\implies$ E is periodic. Only needs to be defined in first Brillouin zone.
                        \end{itemize}
                        \item Density of States $N(E)$
                        \begin{itemize}
                                \item $N(E) = \frac{\Delta N}{\Delta E} = \frac{1}{4\pi^3}\int_S\left(\der{E}{k}\right)^{-1} dS$
                                \item Integral is in momentum space over the isoenergetic surface of energy $E$
                                \item For a free electron gas, $N(E) = $
                        \end{itemize}
                \end{enumerate}
        \end{itemize}

        \item Surface states
        \begin{itemize}
                        \item Simplest model: Step potential
                        \item Two major models  
                \begin{enumerate}
                        \item Tamm States: Periodic potential in solid, free space outside, jump at surface
                        \begin{itemize}
                                \item Energy eigenvalues lie in the forbidden band of the bulk spectra
                                \item Attenuation of eigenvalues from surface to vacuum, oscillation of state within surface
                                \item Max electron density occurs on the crystal surface
                        \end{itemize}
                        \item Shockley states: Potential of surface and bulk cells equal
                        \begin{itemize}
                                \item Corresond to free valences (dangling bonds) at the surface
                        \end{itemize}
                \end{enumerate}
                \item Tamm and Shockley states arise from two extreme models (large change and small change respectively between bulk and surface). In reality, a combination of Tamm and Shockley states appear.
                \item These states arise from termination of the lattice; but the surface cells are assumed undistorted
                \item In reality surface cells are distorted by relaxation and reconstruction of the surface
        \end{itemize}

        \item Main reference: Komolov "Total Current Spectroscopy"
        \item "Solid State Physics" textbooks and "Electron Spectroscopy" textbooks 
\end{itemize}

\subsection{Plasmonics}
I really think I should actually find plasmonic effects before writing too much about them...
\begin{itemize}
        \item Charge density oscillations
        \item Surface and bulk plasmons
        \item Pines and Bohm
        \item Review article from T.W.H Oates et al about using Ellipsometry to characterise plasmonic effects
\end{itemize}

\subsection{Metallic-Black Thin Films}
\begin{itemize}
        \item How they are made (bad vacuum, in air or a noble gas)
        \begin{itemize}
                \item If made in air, there are usually tungsten oxides present (from filament). Refer to paper by Pfund.
        \end{itemize}
        \item Structural difference between Black-Au and ``Shiny'' (need a better term) Au
        \begin{itemize}
                \item Can include electron microscopy images?
                \item An actual photograph of a Black-Au film? Not necessary?
        \end{itemize}
        \item Pfund (earliest publisher, preparation and general properties)
        \item Louis Harris (most research in 50s and 60s)
        \begin{itemize}
                \item L. Harris mostly did transmission spectroscopy in the far infra red (well beyond the ellipsometer and Ocean Optics spectrometer ranges)
                \item The really crappy measurements I did with the Ocean Optics spectrometer seem to agree with these measurements
                \begin{itemize}
                        \item L. Harris' $\lambda$ has a range of 1nm to $100\mu$m; my measurements are only to $1\mu$m
                        \item Agreement in first $1\mu$m anyway
                        \item I should probably re-do those measurements with a less crappy setup, if I actually want to use them
                \end{itemize}
                \item Harris related the optical properties to the structure of the film (condensor strands) via the electronic properties
        \end{itemize}
        \item Plasmonic effects - Deep R. Panjwani (honours thesis)
        \begin{itemize}
                \item Not sure if I can use an honours thesis as a reference.
                \item Concluded that surface plasmon resonance in Black-Au film on solar cells lead to increase in solar cell efficiency
                \item Used simulation that modelled Black-Au film as spherical balls to show E field increased by plasmon resonance
                \begin{itemize}
                        \item Was this model appropriate? Black-Au is more ``smoke'' or ``strand'' like according to other references. Images also do not show ``blob'' like structure.
                \end{itemize}
                \item Need to read this reference more thoroughly
        \end{itemize}
\end{itemize}

\section{Experimental Techniques}

\subsection{Preparation of samples}
\begin{itemize}
        \item Black-Au - 1e-2 mbar vacuum
        \item ``Shiny'' - 1e-6 / 1e-7
        \item Current of ~3.5A through W wire filament spot welded onto Ta strips in turn spot welded to Mo posts
        \item Voltage through filament is ~1 V; quote the power?
        \item Filament isotropically coats sample with desired material.
        \item Possibly get a curve of Au thickness estimated with Ellipsometry vs exposure time?
        \begin{itemize}
                \item Probably too much work and too unreliable
                \item Maybe do it, but only use 2/3 data points
                \item Low priority
        \end{itemize}
\end{itemize}

\subsection{Secondary Electron Spectroscopy}

Secondary electron spectroscopy methods are a broad class of methods which investigate surface electron spectra through observing processes in which the surface electrons participate directly \cite{komolov}. 

Total Current Spectroscopy is a group of electron secondary 

\begin{itemize}
        \item 
        \item Total Current Spectroscopy methods measure the total current of secondary electrons as a function of primary electron energy.
        \item These methods are distinguished from ``differential'' methods (such as Auger electron spectroscopy and energy loss spectroscopy) which measure the secondary electron spectrum at a fixed primary electron energy.
        \item 
        \begin{itemize}
                \item Low energy beam of electrons incident on sample
                \item Measure slope of resulting I-V curve
                \item Relate to density of states and electron band structure (Komolov chapter 3.2)
        \end{itemize}
        \item Description of apparatus
        \begin{itemize}
                \item Electron gun and filament
                \item Electron gun control box
                \item ADC/DAC control box and data processing
        \end{itemize}
        \item Photographs vs Diagrams
        \begin{itemize}
                \item Prefer diagrams to photographs
                \item Especially for the ADC/DAC control box circuit. Because it looks like a horrible mess.
        \end{itemize}
\end{itemize}

\subsection{Ellipsometry and Transmission Spectroscopy}
\begin{itemize}
        \item Overview of techniques
        \item Description of apparatus (use VASE manual)
        \item Ocean Optics spectrometer? Usable?
        \item Application of Ellipsometry to finding plasmonic effects
        \begin{itemize}
                \item Surface plasmons = E oscillation parallel to surface $\implies$ only $p$ component of light excites plasmons
        \end{itemize}
\end{itemize}

\section{Experimental Results and Discussion}
\subsection{TCS Measurements}
\begin{itemize}
        \item TCS for Si
        \item TCS for Si + Au
        \item TCS for Si + Black-Au
        \item Affect of preparation pressure on TCS for Si + Black-Au
        \item Repeat for Si + Ag and Si + Black-Ag (?)
\end{itemize}

\subsection{Ellipsometric Measurements}
\begin{itemize}
        \item Ellipsometry to estimate thickness of SiO2 layer on Si
        \item Estimate thickness of Au/Ag on Si+SiO2
        \item Ellipsometric measurements of Si+Black-Au/Ag
        \begin{itemize}
                \item Modelling procedures to characterise Black-Au/Ag
        \end{itemize}
        \item Ellipsometric measurements of Glass+Black-Au/Ag (?)
        \item Transmission spectra of Glass+Black-Au/Ag from earlier in year (?)
\end{itemize}

\section{Achievements}
\begin{itemize}
        \item Deposition of thin films of Au and Black-Au in vacuum chamber
        \item Ellipsometric and spectroscopic measurements on these films
        \item Repurpose vacuum chamber for sample preparation and TCS experiments
        \item Designed and built electronics for TCS experiments
        \begin{itemize}
                \item Electron gun control box
                \item ADC/DAC box
        \end{itemize}
        \item Wrote software for data aquisition and data processing
\end{itemize}

\section{General notes}
\subsection{TCS}
\begin{itemize}
        \item Optimise setup of gun
        \begin{itemize}
                \item Emission current. How much does it vary, why does it vary.
                \item Why does Is/Ie curve shift with successive sweeps? Does sweep modify sample's surface?
                \item Is sample holder acceptable? Are ceramic washers accumulating charge?
                \item How do I tell when the setup is optimised... 
                ``The setup was optimised by looking for an S curve''. Very scientific.
                \item The gun was focused on the phosphor screen... and then I turned it around, changing the distance from the gun to the sample. Brilliant.
        \end{itemize}
        \item Obtain TCS spectra for Si that compares well with literature
        \begin{itemize}
                \item How to relate TCS spectrum to $n(E)$ and $E(\vect{k})$
        \end{itemize}
        \item Prepare Au films, obtain TCS spectra that compares with literature
        \item Obtain TCS spectra of Black-Au films
        \item Use results to compare properties of films with results from other methods in the literature
        \item Uncertainties
        \begin{itemize}
                \item Oscilloscope measurements of inputs to ADC channels under controlled conditions
                \begin{itemize}
                        \item Expected values are +/-3mV due to ADC channel, +/-300mV due to 610B, +/-1mV due to 602
                        \item 610B and 602 will probably be worse because they are ancient
                        \item There is about 200mV of noise between the GND of the ADC box and the electron control box.
                        \item How to reduce ground loops? Not much I can do. Rack is now also grounded to water pipe, but this doesn't seem to make a difference.
                \end{itemize}
                \item Stupid 50Hz AC noise... how to reduce with filters and/or averaging
        \end{itemize}
        \item Create circuit diagrams for Electron gun circuit
        \item Create circuit diagrams for ADC/DAC box
        \begin{itemize}
                \item Simulate behaviour of circuit
                \item Use of instrumentation amplifier on ADC5 to make off-ground measurements
                \item Use of low pass filter on ADC5
        \end{itemize}
        \item Include references to all datasheets, etc
        \item Vacuum chamber
        \begin{itemize}
                \item Base pressure with rotary pump? Was 1e-3 after 30 minutes at start of year, but probably introduced leaks since then
                \item Lowest pressure achieved with turbo pump is 1.1e-7 mbar as of 25/07.
                \item Viton gaskets on some seals. Copper on other.
                \item Flanges:
                \begin{enumerate}
                        \item View window (large, view of sample \& sputtering filaments)
                        \item Rotation manipulator \& sample mount
                        \item Pump inlet
                        \item Filament flanges 1 (used earlier in year, not anymore) and 2
                        \item Inlet with leak valve (for introducing gases into chamber)
                        \item Vent valve on turbo pump
                        \item Electron gun flange
                        \item View window (small, view of back of electron gun)                 
                \end{enumerate}
        \end{itemize}
\end{itemize}

\section*{Appendix A - Electron Gun Control and Current Measurement Circuit}


\section*{Appendix B - Data Aquisition Box (DAQ)}

\subsection*{Overview}
In order to automate recording of TCS data, a data aquisition box (DAQ) was designed and constructed. The DAQ consists of the following major components:
\begin{itemize}
        \item Microprocessor (AVR Butterfly ATMega169)
        \item Four Analogue to Digital Converter (ADC) inputs
        \item Single Digital to Analogue Converter (DAC) output (Microchip MCP4922)
        \item RS-232 communications for control by a conventional PC or laptop
        \item Seperate Power supplies for digital and analogue electronics
\end{itemize}

\subsection*{Microprocessor}
The DAQ has been built around an Atmel AVR Butterfly; an inexpensive and simple demonstration board for Atmel's ATMega169 16 Bit microprocessor. The features of the AVR Butterfly include easily accessible ports for Analogue to Digital Convertor (ADC) inputs and digital input/output, an onboard Universal Asynchronous Reciever/Transmitter (USART) for RS-232 serial communications, and a 6 character Liquid Crystal Display (LCD). The AVR Butterfly can be programmed using a conventional computer over the USART using a RS-232 COM port. For modern computers (which do not usually posess COM ports), a RS-232 to USB converter may be used.

%Figure of Butterfly




\subsection*{Power Supplies}
Two seperate power supplies are required for the DAQ, due to the presence of both digital and analogue electronics.

\subsubsection*{Logic Power Supply}
The AVR Butterfly runs off $3V < V_{cc} < 5V$ DC. Since $V_{cc}$ is also used as the reference voltage for the ADCs and DAC output, it is desirable that $V_{cc}$ be kept constant, despite the absolute level of the power supply. A $3.3V$ voltage regulator has been used for this purpose. The capacitor further smooths the output by shorting high frequency fluctuations to ground.

When the DAQ was first constructed $V_{cc}$ was supplied by three $1.5V$ batteries. However, due to higher than expected power usage, and the unreliability of the voltage regulator as the input voltage fell below $4V$, inputs for an external power supply were later added.

\subsubsection*{Op-amp Power Supply}
The DAQ circuitry involves several operational amplifiers (LF356), which require dual $\pm 10-15V$ supplies. As there were no dual $\pm$ power supplies available, a single $30V$ power supply was used, with the circuit shown in figure \ref{fig_opamp_supply} used to produce $\pm 15V$ relative to ground.

The buffer amplifier ensures that negligable current can flow from the power supply into the logic and ADC circuits, whilst the capacitor removes high frequency fluctuations of the power supply relative to ground.

To simplify circuit diagrams, op-amps will be drawn with the power supply connections ommitted from this point onwards.

\subsection*{ADC Inputs}
The AVR Butterfly offers easy access to four of the ATMega169's ADCs through PORTF. Each ADC is capable of measuring voltages (relative to ground) of $0 < V_{\text{adc}} < V_{cc}$ with 10 Bit resolution. A voltage divider constructed using a variable resistor allows manual adjustment of $V_{\text{adc}}$ so that voltages greater than $V_{cc}$ may still be measured.  Diodes between the ADC input, and $V_{cc}$ and ground, ensure that the ADC is protected from exposure to voltages outside the acceptable range. Figure \ref{fig_ADC_normal} shows the typical input circuit, used for three of the four available ADCs. 

The voltage at the ADC input can be related to the input of the voltage divider using Kirchoff's Voltage Law and Ohm's Law:
\begin{align*}
 V_{\text{adc}} &= \frac{R_1}{R_1 + R_2} V_{\text{in}}
\end{align*}
Where $V_{\text{in}}$ is the voltage at the input of the circuit, $R_1$ is a fixed resistor, and $R_2$ is variable resistor.

$V_{\text{in}}$ can be determined from ADC counts by:
\begin{align*}
        V_{\text{in}} &= \frac{\text{ADC counts}}{2^{10}} \times 
\end{align*}



For differential or ``off-ground'' voltage measurements, the fourth ADC input is passed through an instrumentation amplifier. Low pass filters on the input are used to reduce AC noise on the inputs. The buffer amplifiers ensure that negligable current flows through the measurement circuit to ground.
Figure \ref{fig_ADC5} shows the input circuit for off-ground voltage measurements. It is important to note that the circuit only functions when the input voltages are within the op-amp common-mode voltage range ($\pm15V$).

The output of the instrumentation amplifier can be shown by using Kirchoff's Laws and the ideal model of op-amps to be:
\begin{align*}
        V_{\text{diff.}} = \frac{R_2}{R_1} 
\end{align*}

\subsection*{DAC Output}
A commercial DAC board was used to produce the DAC output. The Microchip MCP4922 ET-Mini DAC is controlled by the AVR Butterfly using Motorola's Serial Peripheral Interface (SPI) Bus.

The ET-Mini DAC can only be powered off $3V$ to $5V$. Using $V_{cc} = 3.3V$ means that the DAC output cannot exceed $V_{cc} = 3.3V$. For Total Current Spectroscopy, energies of up to $15eV$ are required, so amplification of the DAC output was clearly necessary. A simple non-inverting amplifier with a manually adjustable gain was used to amplify the $3.3V$ DAC output to $10V$. This output was then used to control a GW-Instek GPS-1850D power supply.

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