List of
Figures
1 Introduction
Figure 1.1 The structure of diamond
Figure 1.2 The structure of graphite
Figure 1.3 Buckminster Fullerene, C60
Figure 1.4 The phase diagram of carbon
Figure 1.5 An energy diagram of selected
states in
the band gap of diamond
2 Growth and
Characterisation
Figure 2.1 A schematic diagram of the gas
lines which fed the diamond CVD chamber
Figure 2.2 A photograph of the diborane
dilution assembly
Figure 2.3 A photograph of the deposition
chamber
Figure 2.4 A photograph of the deposition
chamber showing the internal assembly after a deposition run
Figure 2.5 A schematic diagram of a three
layer metal top contact
Figure 2.6 A schematic diagram of a single
layer metal bottom contact
Figure 2.7 A positive ion time-of-flight SIMS
spectrum
Figure 2.8 A negative ion time-of-flight SIMS
spectrum
Figure 2.9 A positive ion time-of-flight SIMS
spectrum (a)
Figure 2.10 A positive ion time-of-flight SIMS
spectrum (b)
Figure 2.11 A positive ion time-of-flight SIMS
spectrum (c)
Figure 2.12 A positive ion time-of-flight SIMS
spectrum (d)
Figure 2.13 A positive ion time-of-flight SIMS
spectrum of the graphite control
Figure 2.14 SIMS spectra plotted relative to the undoped
control sample (a)
Figure 2.15 The surface of a HFCVD diamond film
showing a square facets and a twinned crystallite [B13]
Figure 2.16 The surface of a HFCVD diamond film
[B13]
Figure 2.17 The surface of a HFCVD diamond film
showing uniform coverage over the substrate [B13]
Figure 2.18 A cross-section of a diamond film
[B13]
Figure 2.19 A diamond film grown in an atmosphere
containing 1.4% methane [sample B6]
Figure 2.20 A diamond film grown in an atmosphere
containing 2.8% methane [sample B8]
Figure 2.21 A cross-sectional view of a diamond
films grown with quadruple the normal concentration of methane in the gas phase
[sample B8]
Figure 2.22 A cross-sectional view of an early
run [B1]
Figure 2.23 A continuous diamond film [sample
B142a]
Figure 2.24 Incomplete surface coverage at the
edge of a thin diamond film [sample B142a]
Figure 2.25 Individual crystallites that have
started to coalesce to form a continuous film [sample B142a]
Figure 2.26 Industrial MPACVD diamond (undoped)
Figure 2.27 Industrial MPACVD diamond (undoped)
Figure 2.28 A cross-section of a free-standing
industrial MPACVD diamond film
Figure 2.29 SEM image showing large crystallites
[B141b]
Figure 2.30 SEM image showing growth of a thin
diamond film [sample B141b]
Figure 2.31 SEM image showing a cross-section of
a thin diamond film [sample B141b]
Figure 2.32 A schematic diagram of sample B147a
Figure 2.33 optical microscopy image of the
central section (zone 3) 50 ´ objective lens [sample
B147a]
Figure 2.34 optical microscopy image of the
central section (zone 3) 50 ´ objective lens [sample
B147a]
Figure 2.35 optical microscopy image of the
central section (zone 3) 50 ´ objective lens [sample
B147a]
Figure 2.36 optical microscopy image of the
central section (zone 3) 50 ´ objective lens [sample
B147a]
Figure 2.37 optical microscopy image of the
central section (zone 3) 20 ´ objective lens [sample
B147a]
Figure 2.38 SEM image of the central section (zone
3) [sample B147a]
Figure 2.39 SEM image of the central section (zone
3) [sample B147a]
Figure 2.40 optical microscopy image of an end
sections (zone 5) 50 ´ objective lens showing
limited diamond growth [sample B147a]
Figure 2.41 optical microscopy image of an end
sections (zone 5) 50 ´ objective lens showing
limited diamond growth [sample B147a]
Figure 2.42 optical microscopy image showing
partial diamond growth, 50 ´ objective lens [B147a]
Figure 2.43 optical microscopy image of an end
sections (zone 5) 20 ´ objective lens [sample B147a]
Figure 2.44 SEM image of a diamond end sections (zone
5) [sample B147a]
Figure 2.45 SEM image of one of the isolated
diamond crystallites [sample B147a]
Figure 2.46 optical microscopy image of an
sections (zone 1) 50 ´ objective lens showing partial
diamond growth [sample B147a]
Figure 2.47 optical microscopy image of an
sections (zone 1) 50 ´ objective lens showing
partial diamond growth [sample B147a]
Figure 2.48 optical microscopy image of an end
section (zone 1) 20 ´ objective lens showing
partial diamond growth [sample B147a]
Figure 2.49 optical microscopy image of an end
section (zone 1) 20 ´ objective lens showing
partial diamond growth [sample B147a]
Figure 2.50 SEM image of one a end sections (zone
1) showing partial diamond growth [sample B147a]
Figure 2.51 the boundary between zones 4 and 5 (´ 20 lens) [sample B147a]
Figure 2.52 the boundary between zones 4 and 5 (´ 10 lens) [sample B147a]
Figure 2.53 the boundary between zones 1 and 2 (´ 10 lens) [sample B147a]
Figure 2.54 the boundary between zones 1 and 2 (´ 10 lens) [sample B147a]
Figure 2.55 the boundary between zones 3 and 4 (´ 20 lens) [sample B147a]
Figure 2.56 the boundary between zones 2 and 3 (´ 20 lens) [sample B147a]
Figure 2.57 the boundary between zones 2 and 3 (´ 10 lens) [sample B147a]
Figure 2.58 SEM image of the boundary between zones
4 and 5 [sample B147a]
Figure 2.59 SEM image of the boundary between zones
1 and 2 [sample B147a]
Figure 2.60 SEM image of the boundary between zones
1 and 2 [sample B147a]
Figure 2.61 Raman spectrum of a type IIb natural
diamond
Figure 2.62 Raman spectrum of a poor quality
undoped MPACVD diamond film
Figure 2.63 Raman spectrum of boron doped diamond
[sample B128a]
Figure 2.64 Raman spectrum of boron doped diamond
[sample B128b]
Figure 2.65 Raman spectrum of boron doped diamond
[sample B129a]
Figure 2.66 Raman spectrum of boron doped diamond
[sample B130b]
Figure 2.67 Raman spectrum of boron doped diamond
[sample B140a]
Figure 2.68 Raman spectrum of boron doped diamond
[sample B140b]
3 Electrical
Contacts
Figure 3.1 The Metal-Semiconductor Interface
Figure 3.2 A schematic diagram of the
evaporator
Figure 3.3 Current-Voltage characteristics for
a moderately doped diamond film, 2 Ag dag contacts [B111]
Figure 3.4 Current-Voltage characteristics for
a low doped diamond film with 2 Ag dag contacts [B112]
Figure 3.5 Current-Voltage characteristics
[B111 & B112]
Figure 3.6 Current-Voltage characteristics for
low doped films, 2 Au contacts [B128a & B128b]
Figure 3.7 Current-Voltage characteristics for
oxidised films, 2 Au contacts [B123a & B123b]
Figure 3.8 Current-Voltage characteristics, 3LM contacts [sample B122]
Figure 3.9 Current-Voltage characteristics, TiUL contacts [sample B174a]
Figure 4.1 Current density as a function of
overpotential for a metal
Figure 4.2 Schematic Energy Diagram for a Metal-Solution Interface
Figure 4.3 Schematic Energy Diagram for a Semiconductor-Solution Interface
Figure 4.4 Current density as a function of
overpotential for a semiconductor
Figure 4.5 Schematic Energy Diagram for a Heavily Doped Semiconductor-Solution Interface
Figure 4.6 Current density as a function of
overpotential for a heavily doped semiconductor
Figure 4.8 Forward Bias and Conventional Electrochemical Current
Figure 4.9 Schematic Energy Diagram at positive potential
Figure 5.1 A schematic diagram of an
electrochemistry cell
Figure 5.2 A schematic diagram of a reference
electrode
Figure 5.3 A schematic diagram of a Pt counter
electrode
Figure 5.4 CV 1 M HNO3, 2 M NaCl, 50 mV/s [B67]
Figure 5.5 CV 3 mM 4-aminophenol, 0.5 M H2SO4
[B67]
Figure 5.6 CV 3 mM C6H7NO,0.5
M H2SO4 50
mV/s [B67]
Figure 5.7 CV 3 mM K4[Fe(CN)6],
1 M KCl [B69]
Figure 5.8 CV 3 mM K4[Fe(CN)6],
1 M KCl 50 mV/s [B69]
Figure 5.9 CV 3 mM K4[Fe(CN)6]
…, day 1 [B107]
Figure 5.10 CV 3 mM K4[Fe(CN)6]
…, day 4 [B107]
Figure 5.11 CV 3 mM K4[Fe(CN)6]
…, day 7 [B107]
Figure 5.12 CV 3 mM K4[Fe(CN)6]
…, all days [B107]
Figure 5.13 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+ [B107]
Figure 5.14 CV Fe2+/ Fe3+, 50 mV/s [B107]
Figure 5.15 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+ [Pt WE]
Figure 5.16 CV Fe2+/ Fe3+, compare sample B107 with Pt
Figure 5.17 Mott-Schottky plots [sample B107]
Figure 5.18 AC Impedance plot, Mod(Z) [sample
B107]
Figure 5.19 AC Impedance plot, q [sample B107]
Figure 5.20 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+ [B102]
Figure 5.21 CV Fe2+/ Fe3+, 5 mV/s [B102]
Figure 5.22 AC Impedance plot, Mod(Z) [sample
B102]
Figure 5.23 AC Impedance plot, q [sample B102]
Figure 5.25 AC Impedance, bode plots, concn
expts [B102]
Figure 6.1 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+, O
term, 3LM contact, all rates [B131a]
Figure 6.2 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+, O
term, 3LM contact, 5 mV/s [B131a]
Figure 6.3 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+, 50
mV/s [Pt WE]
Figure 6.4 CV 10 mM Fe2+, 10 mM Fe3+,
1 M H+, 50
mV/s [B131a & Pt WE]
Figure 6.5 CV 0.3 mM Fe(CN)63-, 0.3
mM Fe(CN)64-, 1 M Cl-,
O term, 3LM [B131a]
Figure 6.6 CV 0.3 mM Fe(CN)63-, 0.3
mM Fe(CN)64-, 1 M Cl-,
O term, 5 mV/s, 3LM [B131a]
Figure 6.7 CV 0.3 mM Fe(CN)63-, 0.3
mM, Fe(CN)64-, 1 M Cl-,
50 mV/s, 3LM [Pt WE]
Figure 6.8 CV 0.3 mM Fe(CN)63-, 0.3
mM, Fe(CN)64-, 1 M Cl-,
50 mV/s [B131a & Pt WE]
Figure 6.9 CV 0.3 mM Fe(CN)63-, 0.3
mM, Fe(CN)64-, 1 M Cl-,
O term, 3LM, all rates [B129b]
Figure 6.10 CV 0.3 mM Fe(CN)63-, 0.3
mM, Fe(CN)64-, 1 M Cl-,
O term, 3LM, 25 mV/s [B129b]
Figure 6.11 CV 10 mM Eu3+, 1 M, H+, 1 M Cl-,
O term, 3LM, all rates [B129b]
Figure 6.12 CV 10 mM Eu3+, 1 M, H+, 1 M Cl-,
O term, 3LM, 5 mV/s [B129b]
Figure 6.13 CV 10 mM Fe(CN)63-, 10 mM,
Fe(CN)64-, 1 M Cl-,
H term, TiUL, all rates [B144a]
Figure 6.14 CV 10 mM Fe(CN)63-, 10 mM,
Fe(CN)64-, 1 M Cl-,
H term, TiUL, 5 mV/s [B144a]
Figure 6.15 CV 10 mM Fe(CN)63- / Fe(CN)64-,1
M Cl-, H term, TiUL,
all rates, day 3 [B144a]
Figure 6.16 CV 10 mM Fe(CN)63- / Fe(CN)64-,1
M Cl-, H term, TiUL,
5 mV/s, day 3 [B144a]
Figure 6.17 CV 10 mM Fe2+, 10 mM Fe3+,1 M H+, 3LM, all rates,
day 3 [B134b]
Figure 6.18 CV 10 mM Fe2+, 10 mM Fe3+,1 M H+, 3LM, 100 mV/s,
day 3 [B134b]
Figure 6.19 CV 10 mM Fe(CN)63-, 10 mM,
Fe(CN)64-, 1 M Cl-,
3LM, all rates [B134b]
Figure 6.20 CV 10 mM Fe(CN)63-, 10 mM,
Fe(CN)64-, 1 M Cl-,
3LM, 25 mV/s [B134b]
Figure 6.21 CV 10 mM Fe(CN)63- / Fe(CN)64-,
1 M Cl-, 3LM, 200 mV/s, effect of exposure [B134b]
Figure 6.22 CV 10 mM Fe(CN)63- / Fe(CN)64-,
1 M Cl-, 3LM, all rates, fresh area exposed [B134b]
Figure 6.23 CV 10 mM Fe(CN)63- / Fe(CN)64-,
1 M Cl-, 3LM, 5 mV/s, fresh area exposed [B134b]
Figure 6.24 CV 10 mM Fe(CN)63-, 10 mM,
Fe(CN)64-, 1 M OH-, 3LM, all rates [B134b]
Figure 6.25 CV 10 mM Fe(CN)63-, 10 mM,
Fe(CN)64-, 1 M OH-, 3LM, 5 mV/s [B134b]
Figure 6.26 CV 10 mM Fe(CN)63- / Fe(CN)64-,1
M Cl-, 3LM,
200 mV/s, effect of oxidation [B134b]
Figure 6.27 CV 10 mM Fe(CN)63- / Fe(CN)64-,1
M Cl-, 3LM,
100 mV/s, effect of oxidation [B134b]
Figure 6.28 CV 10 mM Fe(CN)63-, 10 mM Fe(CN)64-,
1 M Cl-, 200
mV/s & 50 mV/s [Pt]
Figure 6.29 CV 10 mM Fe(CN)63-, 10 mM Fe(CN)64-,
1 M Cl-, 50
mV/s [Pt]
Figure 6.30 CV 10 mM Fe(CN)63-, 10 mM Fe(CN)64-,
1 M OH-, 200
mV/s & 50 mV/s [Pt]
Figure 6.31 CV 10 mM Fe(CN)63-, 10 mM Fe(CN)64-,
1 M OH-, 50
mV/s [Pt]
Figure 6.32 CV 10 mM Fe(CN)63-, 10 mM Fe(CN)64-,
1 M OH- or 1
M Cl- 50 mV/s [Pt]
Figure 6.33 CV 1 M Cl-, equimolar Fe(CN)63- & Fe(CN)64-
100 mV/s, concentration experiment [B146b]
Figure 6.34 Mott-Schottky plots, O term, 3LM
[B134b]
Figure 7.1 Energy level diagram showing the
band edges and the energy levels of redox species
Figure 7.2 Reaction at a Hydrogen Terminated
Surface
Figure 7.3 Reaction at an Oxygen Terminated
Surface
Figure 7.4 Equivalent circuit for surface
mediated transfer
Figure 7.5 Mathcad plot of the j - dV relationship case where |j0H| >> |j|
Figure 7.6 Mathcad plot of the j - dV relationship case where |j0H| << |j|
Figure 7.7 Mathcad plot of the j - dV relationship case where |j0H| << |j|
Figure 7.8 Mathcad plot of the j - dV relationship case where |j0SC| >> |j| and j » j0H
Figure 7.9 Mathcad plot of the j - dV relationship intermediate values
Figure 7.10 Mathcad plot of the j - dV relationship intermediate values
Figure 7.11 Mathcad plot of the j - dV relationship comparison, small scale
Figure 7.12 Mathcad plot of the j - dV relationship comparison, large scale
Figure 7.13 Mathcad plot of the j - dV relationship
Figure 7.14 Mathcad plot of impedance equation for
open circuit conditions
Figure 7.15 Mathcad plot of impedance equation at
various potentials
Figure 8.1 The IMPS Set-up
Figure 8.2 IMPS, 1 mM Fe2+, 1 mM Fe3+,
1 M H+ 470 nm [B121a]
Figure 8.3 IMPS, 1 mM Fe2+, 1 mM Fe3+,
1 M H+ 430 nm [B121a]
Figure 8.4 IMPS, 1 mM Fe2+, 1 M H+,
470 nm [B121a]
Figure 8.5 IMPS, 1 mM Fe2+, 1 M H+,
430 nm [B121a]
Figure 8.6 IMPS, 1 mM Fe3+, 1 M H+,
470 nm [B121a]
Figure 8.7 IMPS, 1 mM Fe3+, 1 M H+,
430 nm [B121a]
Figure 8.8 IMPS, near OCP, 770 nm & 730 nm
[B121a]
Figure 8.9 IMPS, near OCP, 730 nm [B121a]
Figure 8.10 Diagram of photogenerated electrons at
the diamond-electrolyte interface
Figure 8.11 Mathcad plot of the j - dV relationship (dark and illuminated)
Figure 8.12 Mathcad plot of IMPS equation