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 Preface

It has been nearly ten years since we began to build an international

consortium in the area of diamond electrochemistry, with our First
International Mini-Symposium, held in Tokyo in 1997. Since that time,
we have tried to keep this tradition going. In addition, there have been
International Symposia on Diamond Materials every two years, held
under the auspices of the Electrochemical Society, with a strong
complement of presentations in the area of electrochemical apphcations
of conductive diamond. These symposia, together with others, such as
the European Conferences on Diamond and Diamond-Like Materials
and the International Conferences on New Diamond Science and
Technology, held in the Eastern Hemisphere, have kept this field
growing at a rapid rate. Almost every aspect of electrochemistry has
been impacted by the diamond electrode, from electroanalysis to
electrolysis.
Recently also, the field has started to mature, with the
development of many practical apphcations of diamond electrodes.
Some of these are being commercialized at present. Two examples are
the diamond electrochemical detector for liquid chromatography and
the large-scale diamond electrode for industrial wastewater treatment.
For the present volume, we have invited representatives fi^om
nearly every group in the world that has been active in the field, and
we are very pleased that many of these groups have responded with
chapters devoted to both their own work as well as that of others.
VI

Certainly we realize that it is virtually impossible to capture

everything that is going on in any given field at a particular time, but
our group of authors has tried hard to accompUsh the impossible.
In Chapter 1, Rao, et al., have provided a historical introduction
to the area, which got its start in 1983 in Japan in a pubUcation by
Iwaki et al. In Chapter 2, Ivandini, et al., provide fiirther historical
perspective and introduce the basics of the preparation and
characterization of chemical vapor-deposited (CVD) diamond films. In
Chapter 3, Martin, et al., discuss several fimdamental aspects of
diamond electrochemistry, including the large working potential range
("wide potential window"), aspects of the reactivity, the optical
transparency, semiconductor aspects, and the surface conductivity
phenomenon. In Chapter 4, Pleskov gives a fuU account of the
semiconductor aspects of diamond electrochemistry. In Chapter 5,
Levy-Clement focuses on the role of the boron doping level in
determining the electrochemical properties, together with Raman
spectroscopy as a useful diagnostic tool in estimating the effective
doping level. In Chapter 6, Yoshimura et al. examine the factors that
determine the potential working range for various non-aqueous
solvent/electrolyte systems, including theoretical molecular orbital
calculations. In Chapter 7, Yagi, et al., examine the use of a novel
technique, time-of-flight electron-stimulated desorption, as a means of
understanding the interactions of the diamond surface with hydrogen,
the most important of the surface terminations. In Chapter 8, Kondo,
et al., examine the electrochemistry of single-crystaMike homoepitaxial
diamond films, particularly as nearly ideal electrodes for
electroanalytical apphcations. In Chapter 9, Tryk, et al., review the
various techniques available for the chemical modification of the
 Preface vii

diamond surface, including ways of attaching DNA strands. In

Chapter 10, Notsu, et al., focus on the oxidized diamond surface, which
is the most common form of chemically modified diamond surface. In
Chapter 11, Einaga, et al., present several different ways of producing
functional diamond surfaces, including diamond microelectrode arrays,
diamond surfaces ion-implanted with metals to impart catalytic
activity, and ultrasmooth diamond surfaces produced by the glow
discharge technique. In Chapter 13, Spataru, et al., focus on the
advantages of the diamond electrode for the oxidative determination of
various types of biologically active compounds. In Chapter 14, Shin, et
al., discuss the use of the boron-diamond electrode as a detector for
capiUary zone eletrophoresis, which is quickly becoming a powerful
technique for the detection of a number of different types of compound
mixtures, for example, explosives, as well as biologically active
compounds such as neurotransmitters. In Chapter 15, Orawon, et al.,
discuss the use of diamond electrodes for the determination of the
biologically important suLfur-containing compounds. In Chapter 16,
Manivannan, et al., examine the diamond electrode for use in the
detection of trace concentrations of toxic metals. In Chapter 17,
Suryanarayanan, et al., examine several diverse examples of analytical
apphcations of boron-doped diamond electrodes for industrially
important chemicals. In Chapter 18, Ohvia, et al., present the topic of
boron-doped diamond microelectrodes, which are highly interesting
and analytically useful, because they combine the advantages of
diamond with those of the microelectrode, including efficient mass
transport. In Chapter 19, Honda and Fujishima discuss the highly
interesting nanotextured diamond surfaces, along with possible
apphcations of such electrodes. In Chapter 20, ComnineUis, et al..
Vlll

discuss the use of hydroxyl radicals generated at the diamond surface

to carry out various types of oxidation reactions, including
electrosynthetic processes, and the electrochemical "combustion" of
organic compounds. In Chapter 21, Vatistas, et al., examine a highly
useful approach to the use of diamond for wastewater treatment, i.e.,
involving the electrogeneration of hydroxyl radicals, followed by the
reaction of these radicals with inorganic ions such as sulfate to produce
active oxidants, circumventing the mass transport problems associated
with the direct reaction of hydroxyl radicals with pollutants. In
Chapter 22, Cho, et al., focus on the use of diamond electrodes for the
electrogeneration of ozone, which is an important oxidant and potential
replacement for chlorine. In Chapter 23, Furuta, et al., provide a very
interesting account of the practical use of diamond electrodes in
ordinary tap water to produce oxidants that are capable of destroying
the bacteria that cause Legionnaires' Disease. In Chapter 24, Arihara
and Fujishima provide an additional account of how diamond
electrodes, specifically, free-standing ones, can be used successfully to
produce ozone-water, which is an environmentally fidendly decolorizing
and antibacterial agent. Finally, in Chapter 25, Rao, et al., provide a
summary and perspective on the fundamental and apphed aspects of
diamond electrodes.
Lastly, we would very much hke to acknowledge the great
contribution of Dr. Ivandini Tribidasari in assembhng this volume,
which could not have been completed otherwise.

Akira Fujishima
 IX

The Editors

Professor Akira Fujishima

Professor Fujishima was born in 1942 in Tokyo. He
received his Ph. D. in AppHed Chemistry at the
University of Tokyo in 1971. He taught at Kanagawa
University for four years and then moved to the
University of Tokyo, where he became a Professor in
1986. In 2003, he retired from this position and took on
the position of Chairman at the Kanagawa Academy of
Science and Technology. His main interests are in photocatalysis,
photoelectrochemistry and diamond electrochemistry.
[Kanagawa Academy of science and Technology, KSP 3-2-1 Sakado, Kawasaki
213-0012, Japan, E-mail- [email protected]]

Professor Yasuaki Einaga

Professor Einaga was born in Niigata Prefecture,
J a p a n in 1971. He received his Ph.D degree in 1999
from The University of Tokyo under the direction of
Prof. Akira Fujishima. He joined the Department of
Chemistry at Keio University as an Assistant
Professor in 2001. In 2003, he was promoted to
Associate Professor. His research interests include
photo-functional materials science and diamond electrochemistry.
[Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Yokohama 223-
8522, Japan, E-mail- [email protected]]
 Dr. Tata Narasinga Rao
Dr. Rao was born in India in 1963. He received his
Ph.D. degree in 1994 from Banaras Hindu Unversity,
India. After working at IIT Madras, he moved to The
University of Tokyo as a J S P S Postdoctoral Fellow
and became an Assistant Professor in 2001. Presently,
he is a senior scientist at the International Advanced
Research Centre for Powder Metallurgy and New
Materials (ARCI) in Hyderabad, India. His research interests include
diamond electrochemistry, nanomaterials synthesis and their applications for
environmental remediation.
[International Advanced Research Centre for Powder Metallurgy and New
Materials. Balapur PO, Hyderabad 500005, India, E-mail : tatanrao@yahoo.
com]

Dr. Donald A. Tryk

Dr. Donald Tryk was born in California (USA) in 1948
and received his Ph. D. in Chemistry from the
University of New Mexico in 1980. He was with the
Yeager Center for Electrochemical Sciences at Case
Western Reserve University in Ohio (USA) before
joining Prof. Fujishima's group in 1995. After two
2^^^ years at Tokyo Metropolitan University, he is now at
the University of Puerto Rico. His interests are diamond electrochemistry
and electrocatalysis.
[Department of Chemistry, University of Puerto Rico, Rio Piedras Campus,
San J u a n , Puerto Rico 00931-3346, E-mail •' [email protected]]

Special Thanks for Contribution

Dr. Ivandini Tribidasari Anggraningrum
Dr. Ivandini was born in Indonesia in 1970 and received her
Ph. D. from the University of Tokyo in 2003. She is a
lecturer in the Department of Chemistry, Mathematics and
Science Faculty, University of Indonesia in Jakarta,
Indonesia. Now, she is doing post-doctoral research
supported by a JSPS award at the Department of Chemistry,
Keio University, Japan. Her interest is in diamond
electrochemistry.
 XI

List of Authors

John. C. Angus
Case Western Reserve University, USA
Kazuki Arihara
Central J a p a n Railway Company, J a p a n
Oraw^on Chailapakul
Chulalongkorn University, Thailand
Eun-In Cho
Chungbuk National University, Korea
Christos Comninellis
Swiss Federal Institute of Technology, Switzerland
Ilaria Duo
Swiss Federal Institute of Technology, Switzerland
Sally C. Eaton
Case Western Reserve University, USA
Yasuaki Einaga
Keio University, J a p a n
Akira Fujishima
Kanagawa Academy of science and Technology, J a p a n
Tsuneto Furuta
Permelec Electrode Ltd., J a p a n
Werner Haenni
Centre Suisse d'Electronique et de Microtechnique SA (CSEM),
Switzerland
Olivia Herlambang
Canon Inc., J a p a n
Kensuke Honda
Yamaguchi University, J a p a n
Tribidasari A. Ivandini
University of Indonesia, Indonesia
Takeshi Kondo
Tokyo University of Science, J a p a n
Uziel Landau
Xll

Case Western Reserve University, USA

Claude LevyClement
CNRS, France
Ayyakannu Manivannan
West Virginia University, USA
Beatrice Marselli
Swiss Federal Institute of Technology, Switzerland
Heidi B. Martin
Case Western Reserve University, USA
Hideki Masuda
Tokyo Metropolitan University, J a p a n
Pierre "Alain Michaud
Swiss Federal Institute of Technology, Switzerland
Yoshinori Nishiki
Permelec Electrode Ltd., J a p a n
Hideo Notsu
The University of Tokyo, J a p a n
Soo-Gil Park
Chungbuk National University, Korea
Su-Moon Park
Pohang University of Science &; Technology, Korea
Jong-Eun Park
Chungbuk National University, Korea
Gebriele Prosper!
University of Pisa, Italy
Yuri V. Pleskov
Frumkin Institute of Electrochemistry, Russia
Laurent Pupunat
Centre Suisse d'Electronique et de Microtechnique SA (CSEM),
Switzerland
Tata N. Rao
International Advanced Research Centre for Powder Metallurgy and
New Materials, India
Philippe Rychen
Centre Suisse d'Electronique et de Microtechnique SA (CSEM),
Switzerland
 List of Authors xiii

Bulusu V. Sarada
The University of Tokyo, J a p a n
Roberto Massahiro Serikawa
Ebara Research Co. Ltd., J a p a n
Dongchan Shin
National Institute of Advanced Industrial Science and Technology,
Japan
Nicolae Spataru
Institute of Physical Chemistry of the Roumanian Academy, Romania
Vembu Suryanarayanan
Utsunomiya University, J a p a n
Hozumi Tanaka
Permelec Electrode Ltd., J a p a n
Tetsu Tatsuma
The University of Tokyo, J a p a n
Chiaki Terashima
GL Sciences Inc., J a p a n
Donald A. Tryk
University of Puerto Rico, Puerto Rico

Kazuyuki Ueda
Hokkaido University, J a p a n
Kohei Uosaki
Hokkaido University, J a p a n
Nicolaos Vatistas
University of Pisa, Italy
Joseph Wang
New Mexico State University, USA
Ichizo Yagi
Hokkaido University, J a p a n
Sachio Yoshihara
Utsunomiya University, J a p a n
Mikiko Yoshimura
Matsushita Electric Industrial Co. Ltd., J a p a n
Yanrong Zhang
Utsunomiya University, J a p a n
1. Historical Survey of Diamond
Electrodes
Tata N. Rao, Akira Fujishima and John C. Angus

1.1. Introduction

Conductive boron-doped diamond is an alternative to traditional

carbon electrodes that provides superior chemical and dimensional
stability, low background currents, and a very wide potential
window of water stability (Fig. l.l). In this Chapter we describe
the historical development of these unique electrodes.
Traditional carbon electrodes, such as glassy carbon, carbon
fiber, carbon cloth, carbon nanotubes, various forms of disordered
carbon, and graphite are important in electrochemistry because of
low cost, simple preparation methods, possibility of achieving
large surface area, and a relatively wide potential window of
water stability. They have many applications, ranging from Li-ion
batteries and double layer capacitors to electrochemical sensors.
Carbon also plays an important role in fuel cells as a substrate for
dispersal of a small amount of precious metal catalyst over a large
area. Despite their advantages, traditional carbon electrodes still
suffer drawbacks. For example, electrode fouling limits their long
term stability and leads to frequent polishing or disposal of the
electrode after a few uses. The limited potential window for water

Tata N. Rao e-mail: [email protected]

electrolysis prevents the detection of compounds that oxidize at
relatively high anodic potentials. Electrodes exhibiting better
stability and wider potential window are desired for such
applications.

lU - i

5- Glassy carbon
! !
Diamond ^j
>>
u- /:>^ <—•
1 1•
/ <
1 i
-5-
Hg electrode
3

10- 1 \ 1 1

Voltage (V vs. SCE)

Fig. 1.1. Cyclic voltammogram for diamond in 0.1 M H2SO4. The

range of potential windows for glassy carbon and Hg electrodes are
shown for comparison.

Chemical and dimensional stability and wide potential

window are also important for the electrochemical treatment of
wastewater. Traditional carbon electrodes oxidize and are not a
good choice for this application. A wide potential window for
oxygen evolution permits electrogeneration of oxidants such as
hydroxyl radicals from water discharge. Metal oxides, e.g., Sn02
and Pb02, meet these requirements to some extent; however,
electrodes with improved stability, especially in aggressive
environments, are desired for electrochemical treatment
technology.
 1. Historical Survey of Diamond Electrodes

1.2. Origin of Diamond Electrochemistry

In 1983, Japanese scientists at the Institute of Physical and

Chemical Research (RIKEN) in Saitama reported the use of ion-
implanted diamond as an electrochemical electrode [l]. Their
electrode had a wider potential window in the cathodic direction
and lower background than glassy carbon. However, their
diamond was made conductive by ion implantation of Zn, which
resulted in a damaged surface. Although this was the first report
on diamond electrochemistry, it did not lead to other work.
In 1987, Pleskov in Russia used semiconducting diamond
electrodes for photoelectrochemistry [2]. His work generated
interest by photoelectrochemists because the conduction band of
semiconducting diamond is near the vacuum level, leading to the
possibility that diamond can drive photoelectrochemical reduction
reactions requiring very negative potentials such as nitrogen
fixation or deposition of electronegative metals (Fig. 1.2).
Fujishima and coworkers studied the photoelectrochemistry of
diamond in the early nineties [3] and later demonstrated
excitation across the band gap with an Ar-ion laser (193 nm) [4].
This group also showed that changes in the flat-band potential are
due to different surface terminations (oxygen or hydrogen) that
change the band edge positions [5].
In 1993 Tenne et al. reported the application of diamond for
the electroreduction of nitrate to ammonia [6]. Also in 1993,
Ramesham and Swain reported the suitability of diamond for
analytical applications [7], and Ramesham and Loo [8] indicated
the advantage of diamond for dimensionally stable anodes in
electrochemical waste treatment. Subsequently, Martin and
coworkers [9-11] showed that high quality boron-doped electrodes
had an extremely wide potential window of water stability. Miller
et al. [12] reported on the use of implanted diamond as an
electrode, and Carey [13] at Eastman Kodak used diamond
electrodes for the anodic destruction of organic wastes.

-3.04 Li+/Li
-2.70 Hp/e,^.
2.40 N2/NH3OH+

-0.27 H+/H,

Potential vs. SHI

Fig. 1.2. Energy band diagram for diamond showing for comparison
the energies for the various redox couples (at pH 4.5).

These early reports triggered aggressive research that

resulted in a rapid increase in the number of publications, from 4
in 1992 to 121 in 2003 (Fig. 1.3). By the end of 2003, there were
over 386 research reports, mostly on fundamentals and
 1. Historical Survey of Diamond Electrodes

applications related to electroanalysis and electrochemical

treatment. The first patent on electrochemical treatment using
diamond electrodes appeared in 1995 [13]. By 2003 the total
number of patents on diamond electrodes reached 25.
The early work on diamond electrodes is summarized in
several prior reviews [l4"2l].

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Fig. 1.3. Yearly research publications on diamond electrochemistry.

1.3. Recent Directions

The wider potential window (in comparison to glassy carbon) on

the anodic side has enabled the detection of a wide range of
compounds in the anodic region [22-31], and it has allowed the
generation of oxidants such as hydroxyl radicals with high yields
[32-36]. The potential window on the cathodic side, comparable to
that of mercury, allows the detection of trace metals [37-40]. This
enables the replacement of toxic, mercury-based electrodes for
trace metal detection. Furthermore, being chemically stable,
diamond can be used in highly aggressive liquid media [41]. The
electrochemical properties of diamond are sensitive to the surface
termination (oxygen or hydrogen) permitting its application in
modified electrodes [42-45].
Conducting, transparent diamond provides a tool for studying
electrode processes. They have been used for in situ infrared
studies of changes at diamond surfaces during polarization [46]
and for spectroelectrochemical studies of redox systems such as
chlorpromazine and cytochrome c [47].
There is great interest in electrochemical treatment of waste
water using diamond electrodes. In addition to the stability of
these electrodes in corrosive electrolytes, they also exhibit a large
overpotential for oxygen evolution. This permits the production of
strong oxidants, such as ozone and hydroxyl radical [32-36].

1.4. Summary

Diamond electrodes are a major innovation enabling many new

applications in electrochemistry. However, fundamental issues
must be resolved before their full potential can be realized. In the
following Chapters, recent investigations on the properties of
these unique electrodes are summarized.
 1. Historical Survey of Diamond Electrodes

References

1. M. Iwaki, S. Sato, K. Takahashi and H. Sakairi, Nucl. Instrum.

Methods Phys. Res,, 209 (1983) 1129.
2. Y. V. Pleskov, A. Ya. Sakharova, M. Krotova, L. L. Bouilov and B.
V. Spitsyn, J. ElectroanaL Chem., 228 (1987) 19.
3. K. Patel, K. Hashimoto and A. Fujishima, Denki Kagaku, 60
(1992) 659.
4. L. Boonma, T. Yano, D. A. Tryk, K. Hashimoto and A. Fujishima,
J. Electrochem. Soc, 144 (1997) L142.
5. T. N. Rao, D. A. Tryk, K. Hashimoto and A. Fujishima, J.
Electrochem. Soc, 146 (1999) 680.
6. R. Tenne, K. Patel, K. Hashimoto and A. Fujishima, J.
ElectroanaL Chem., 347 (1993) 409.
7. G. M. Swain and R. Ramesham, Anal. Chem., 65 (1993) 345.
8. R. Ramesham, R. F. Askew, M. F. Rose and B. H. Loo, J.
Electrochem. Soc, 140 (1993) 3018.
9. H. B. Martin, A. Argoitia, J. C. Angus, A. B. Anderson and U.
Landau, in "Apphcations of Diamond Films and Related
Materials* Third International Conference," (A. Feldman, et al.,
Eds.), pp. 91-94. NIST Special Publication 885, U.S. Dept. of
Commerce. (1995).
10. H. B. Martin, A. Argoitia, U. Landau, A. B. Anderson and J. C.
Angus, J. Electrochem. Soc 143 (1996) L133.
11. H. B. Martin, J. C. Angus and U. Landau, J. Electrochem. Soc
146 (1999) 2959.
12. B. Miller, R. Kalish, L.C.Feldman, A. Katz, N. Moria, K. Short
and A.E. White, J. Electrochem. Soc, 141 (1994) L41.
13. J. J. Carey, C. S. Christ and S. N. Lowery: US Patent b,^m (1995)
247.
14. G.M. Swain, A.B. Anderson and J.C. Angus, MRS Bull. 23 (1998)
56.
15. R. Tenne and C. Levy-Clement, Isr. J. Chew. 38 (1998) 57.
16. J.C. Angus H.B. Martin, U. Landau., Y.E. Evstefeeva, B. Miller
and N. Vinokur, New Diamond Front Carbon TechnoL 9 (1999)
175.
17. K. Kobashi, Editor, New Diamond Front Carbon TechnoL 9, Nos.
3&5 (1999).
18. Y. V. Pleskov, Russ. Chem. Rev. 68 (1999) 381.
19. T. N. Rao and A. Fujishima, Diamond Relat Mater. 9 (2000) 384.
20. A. Fujishima and T. N. Rao, Diamond Relat Mater. 10 (2001)
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Fujishima, New Diamond Front Carbon TechnoL 13 (2003) 79.
22. T. N. Rao, I. Yagi, T. Miwa, D. A. Tryk and A. Fujishima, AnaL
Chem., 71 (1999) 2506.
23. J. Xu and G. M. Swam, AnaL Chem., 70 (1998) 1502.
24. M. D. Koppang, M. Witek, J. Blau and G. M. Swain, AnaL Chem.,
71 (1999)1188.
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Fujishima, AnaL Chem. 72 (2000) 1632.
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Fujishima, AnaL Chem., 74 (2002) 895.
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Fujishima, Anal Chem., 74 (2002) 1578.
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29. N. S. Lawrence, M. Thompson, C. Prado, L. Jiang, T. G. J. Jones
and R. G. Compton, Electroanalysis, 14 (2002) 499.
30. C. Prado, G. Flechsig, P. Grundler, J. S. Foord, F. Marken and R.
G. Compton, Analyst (Cambridge UK), 127 (2002) 329.
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Chem., 75 (2003) 1564.
32. M. Panizza, P. A. Michaud, G. Cerisola and Ch. Comninellis, J.
ElectroanaL Chem. 507 (2001) 206.
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Ch. ComnineUis, J. Electrochem. Soc, 148 (2001) D60.
34. B. Boye, P. A. Michaud, B. Marselh, M. M. Dieng, E. Brillas and
Ch. ComnineUis, New Diamond Front Carbon TechnoL 12 (2002)
63.
35. W. Haenni, J. Gobet, A. Perret, L. Pupunat, P. Rychen, Ch.
Comninelhs and B. Correa, Ibid., 12 (2002) 83.
36. I. Troster, L. Schafer and M. Fryda, Ibid., 12 (2002) 89.
37. C. Prado, S. J. Wilkins, F. Marken and R. G. Compton,
Electroanalysis, 14 (2002) 262.
38. A. J. Saterlay, D. F. Tibbetts and R. G. Compton, Anal ScL, 16
(2000) 1055.
39. A. Manivannan, D. A. Tryk and A. Fujishima, Electrochem. Solld-
StateLettl{X^^^)A^^.
40. A. Manivannan, M. S. Seehra, D. A. Tryk and A. Fujishima, Anal
Lett 35 (2002) 355.
41. G. M. Swain, J. Electrochem. Soc, 141 (1994) 3382.
42. H. Notsu, I. Yagi, T. Tatsuma, D. A. Tryk and A. Fujishima, J.
ElectroanaL Chem., 492 (2000) 31.
43. J. Xu, Q. Chen and G. M. Swain, Anal Chew., 70, 3146 (1998).
44. T. A. Ivandini, B. V. Sarada, T. N. Rao and A. Fujishima, Analyst,
128 (2003) 924.
45. T. C. Kuo, R. L. McCreery and G. M. Swain, Electrochem. Solid-
StateLett, 2 (1999) 288.
46. H. B. Martin and P. W. Morrison Jr., Electrochem. SolidState
Lett.,Ai20{)l)E-ll.
47. J. Stotter, S. Raymond, J.K. Zak, Y. Show, Z. Cvackova and G. M.
Swain, Interface Spring 33 (2003).

10
2. Preparation and Characterization
of Poly crystalline Chemical Vapor
Deposited Boron-doped Diamond
Thin Films
Tribidasari A. Ivandini, Yasuaki Einaga, Kensuke Honda and
Akira Fujishima

The development of low-pressure synthesis methods for diamond,

such as the chemical vapor deposition (CVD) technique, has
generated enormous and increasing interest and has extended the
scope of diamond applications. Highly efficient methods have
been developed for the economical growth of poly crystalline
diamond films on non-diamond substrates. Moreover, these
methods allow the controlled incorporation of an impurity such as
boron into diamond, which in this case forms a p-type
semiconductor. By doping the diamond with a high concentration
of boron (B/C = 0.01), conductivity can be increased, and semi-
metallic behavior can be obtained, resulting in a new type of
electrode material with all of the unique properties of diamond,
such as hardness, optical transparency, thermal conductivity and
chemical inertness [1,2].
The low-pressure synthesis involves the conversion of a gas-
phase carbon-containing species into a solid cubic crystalline form,
i.e., diamond. The first reproducible low-pressure diamond

Tribidasari A. Ivandini e-mail: [email protected]

11
synthesis was achieved by use of carbon monoxide as a source gas
to precipitate diamond by Eversole [3]. In 1956, Spitsyn proposed
the growth of diamond at low pressure through the decomposition
of carbon tetraiodide [4], and in 1959, Angus proposed the growth
of diamond at relatively low temperatures, where it is in a meta-
stable state [5]. The growth of diamond on non-diamond
substrates was first accomplished in 1976 in a chemical transport
reaction occurring in a closed system at a pressure below
atmospheric and a substrate temperature of the order of 1000°C
[6]. Rapid growth of diamond at low pressure was then reported
by NIRIM (the National Institute for Research on Inorganic
Materials) in Japan using a hot-filament technique to activate a
CH4/H2 gas mixture [7]. Hydrogen is needed for the continuous
growth of diamond, as atomic hydrogen etches away the graphite
that is coproduced. Oxygen has also found been found to have a
role in etching graphite. In the work described in this Chapter, a
mixture of methane and acetone was used as the carbon source.
For the growth of boron-doped diamond films, the boron doping
agent is generally added as small amounts of diborane, trimethyl
boron, or organic borates in the gas phase [8]; solid-state boron
sources such as boron oxide are also used [9].
Generally, CVD techniques can be classified into three
groups' plasma-assisted CVD, hot filament-assisted CVD, and
combustion flames, as well as combinations of these [l].
This Chapter will focus on the hot-filament and microwave
plasma-assisted CVD techniques, which are the most commonly
employed methods to grow diamond thin films and were used for
most of the experiments described in this book. The major

12
2 Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

advantage of MPACVD is that by simple operation it can easily

give high quality diamond. However, since the plasma area is
limited by the wavelength of the microwave radiation, it is
difficult to achieve a large-area deposition. For example, the
optimum wafer size used in our equipment is 3.5 cm x 3.5 cm
squares, although depositions on 3-to 5-inch (7.6 to 12.7-cm)
wafers with a thickness variance of 10% have been reported [lO].
However, for the deposition of large-area films, which are
necessary for the electrochemical treatment of industrial
wastewater, hot-filament CVD deposition is more suitable. Thin
films with areas as large as 0.5 m^ were deposited on Nb mesh
substrates by use of the hot-filament CVD technique. The
equipment used for the preparation of diamond thin film
electrodes and for their characterization will be discussed.

2.1. Microwave Plasma-Assisted CVD (MPACVD)

In the plasma-assisted technique, diamond growth involves

various forms of plasma-assisted CVD processes with carbon-
containing species mixed in low concentrations with hydrogen.
The main types of plasmas used are (a) the DC plasma, (b) the RF
plasma, (c) the microwave plasma, (d) the electron cyclotron
resonance microwave plasma, and (e) the high-pressure plasma.
The role of the plasma is to generate atomic hydrogen and to
produce the appropriate carbon precursors for the growth of
diamond.
Plasma-assisted deposition is a combination of two processes-
a homogeneous process in the plasma bulk and a heterogeneous

13
process at the plasma-surface boundary. The processes start in the
dissociation of the hydrogen source and the formation of
intermediate species, through the transport to the substrate and
nucleation processes following the stabilization of the sp^ diamond
phase on the surface of the growing film.
The plasma exists when a significant number of atoms or
molecules are electrically charged or ionized by applying an
electromagnetic field across a gas. The energy of the applied
electric field arises mainly from free electrons, and the plasma
achieves a thermodynamic non-equilibrium condition based on the
high electron temperature and low gas temperature. Excitation,
ionization and dissociation of atoms and molecules of the
reactants and of the carrier gases to various radical and ion-
radical species are achieved as a result of a sequence of inelastic
electron-neutral collisions.

2.1.1. Equipment

Microwave
(from magnetron)
Quanz
Window

\
J |4-.H,
Sample
Stage MFC p - — - ® " ^ H:

Rotary
pump

^ t ^ i

Fig. 2.1. Schematic diagram for CVD equipment

14
2 Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

Figure 2.1 shows a schematic diagram of the CVD equipment. A

commercial low-pressure microwave (2.45 GHz) plasma reactor,
Model AX5400 (ASTeX Corp., Woburn, MA) was used (Fig. 2.2).
This unit consists of a vacuum system, a microwave generating
system and a gas supply system.

Control
unit

Bubbling
unit for
carbon
source

Fig. 2.2. Illustration of ASTeXCVD System

The vacuum system consists of a stainless vacuum chamber,

rotary pump (2EM12F, Edwards, Co. Ltd.), inline valve (manual
valve) control valve (248A, MKS Instruments, Inc.), pressure
controller (250C, MKS Instruments, Inc.) and capacitance
manometer (127A, MKS Instruments, Inc.). On the top of the
chamber is a quartz window, which is connected to the magnetron,
which is the microwave source, through the wave-guide. Between
the wave-guide and the quartz window, there is a fixed symmetric

15
p l a s m a coupler, a n d t h i s plays a role in generating t h e p l a s m a a s
a sphere. Inside the chamber, t h e r e is a sample stage, whose
height can be changed by m e a n s of a drive-motor. S u b s t r a t e s are
heated by h e a t irradiation from the plasma, and to m a i n t a i n the
t e m p e r a t u r e of t h e stage, a cooling system is utilized.

Table 2.1. Condition for a deposition of diamond using a microwave

plasma CVD system

Substrate: n-Si(lll)
Carbon Source: Acetone/Methanol (9:1)
Boron Source: Boron trioxide
Excitation Source: Plasma
Substrate Temperature: Ca. 900-1000°C
Total Pressure: llSTorr
C/H ratio: 0.03
Time Deposition: 8 hours
FilmThickness : 40-50 Mm
Sample Size : 35 X 35 mm

The microwave generating system consists of wave generator

(AX2040, ASTex Corp., Woburn, MA), microwave guide and
turners, circular/directional coupler and microwave source
(HS5000, Aster Corp., Woburn, MA). The microwave generator
can generate a microwave p l a s m a with a power up to 5 kW. The
circular/directional coupler protects t h e microwave p l a s m a source
from reflecting microwave radiation. An e n d T a u n c h system is
used w h e n samples exist n e a r t h e bottom of the p l a s m a ball. The
gas supply system consists of m a s s flow controllers (1159B, MKS

16
2. Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

Instruments, Inc.), a power supply (274C, MKS Instruments),

mechanical valves and cylinders. The operating conditions for the
microwave plasma are given in Table 2.1.

2.1.2. Gas Sources

Although the vapor deposition process for diamond utilizes
temperature and pressure conditions under which graphite is the
stable form of carbon, kinetic factors allow diamond to be
produced by a commonly used net chemical reaction-
CH4(g) ^ C (diamond) + 2H2 (2.1)
Generally, methane is used as the carbon source and diborane as
the boron source. In addition to methane, other hydrocarbon
gases can be used. In the present study, a mixture of acetone and
methanol (9-1 volume ratio) was used as the carbon source, in a
recipe first reported by Okano et al. [ l l ] . Diborane is
advantageous since the boron/carbon ratio (B/C) can be changed
by controlling the respective mass flow rates. However, the
explosively reactive nature of this system in the presence of
oxygen requires a special security system. Therefore, it is safer to
use B2O3 than diborane.
Methanol is used in the carbon source since the solubility of
B2O3 in acetone is very low. B2O3 is added to reach a B/C atomic
ratio of 0.01 and the mixture is then ultrasonicated for complete
dissolution. The boron concentration in a film prepared under
these conditions was ca. 1.5 x lO^i cm"3 as estimated by Notsu et
al., based on nuclear reaction measurements [iiB(p,a)^Be], carried
out by means of 1-meV proton bombardment and subsequent
comparison of the alpha spectrum in the 6-8 MeV region with a

17
BN standard [12]. When dissolved in the solution, B2O3 reacts
with methanol, to form a boron ester.
B2O3 + 6CH3OH ^ 2B(OCH3)3 + 3H2O (2.2)
This boron ester has a very high vapor pressure, similar to that
of methanol, and therefore boron is introduced easily. To
introduce acetone and B2O3 more efficiently, hydrogen gas was
used as a carrier gas, by bubbling through the carbon source
liquid.

2.1.3. Pretreatment of Substrates

Many substrates can be used for the growth of diamond. Many
have the characteristic of forming carbides at the interface
between the substrate and the diamond crystal. Si, Mo, W, Ti, Nb
are commonly used substrates for the growth of diamond films. Si
is the most commonly used substrate, because it has a structure
similar to diamond. Nucleation of the substrate is necessary for
the deposition of diamond. Generally, the substrate is either
scratched with abrasive diamond powder or is pretreated with the
abrasive powder under ultrasonic generation.
For example, the Fujishima group at the University of Tokyo
used n-type silicon (lOO) wafers (phosphorus-doped, with a
thickness of 0.625 mm, and a resistivity of 0.005-0.018 Q cm).
Surface pretreatment of the substrate is needed for the efficient
growth of diamond due to the mismatch of the lattice constants for
diamond and silicon. Although no conclusive data has been
published on the mechanism of the nucleation enhancement, it is
widely argued that either sub-micromolar scratches or other

18
2. Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

structural defects at the substrate surface, induced by the

polishing, produce active sites for nucleation [13].
Prior to deposition, silicon substrates were pretreated by
surface polishing with 0.5-^im diamond powder (Type Micron+
SND, De Beers). After polishing, the substrates were rinsed in
2-propranol with ultrasonication.

2.2. Hot Filament-Assisted CVD

Hot filament-assisted CVD has been attracting extensive

attention due to its low expense, the simplicity of apparatus
required and the large area of the diamond films that may be
produced. When the decomposition temperature of the gas phase
is much higher than the growth temperature, a super-equilibrium
of excited species results near the growth region. This is easily
achieved by contacting the gas phase with a filament of refractory
metal, which is heated by an electrical current. A filament form
was chosen to heat the gas phase locally and to avoid overheating
the deposition region and of the equipment.
In hot-filament CVD, the tungsten filament, which is usually
heated above 2000°C, is placed above the substrate heated at 600-
1000°C, on which diamond film is deposited. The research groups
at the Fraunhofer Institute for Surface Engineering and Thin
Films at Braunschweig, CONDIAS GmbH at Itzehoe in Germany,
together with a group at the Swiss Center of Electronic and
Microtechnology (CSEM) at Neuchatel in Switzerland use the
HFCVD method for the deposition of their diamond electrodes.
These research groups have developed the HF-CVD technology for

19
the production of electrodes with a areas up to 0.5 m^ (see Fig.
2.3).
The above research groups produce diamond electrodes
mainly on Si or Nd substrates. CSEM produces diamond films on
Si discs of 100-mm diameter and 1-mm thickness. These
electrodes are preferred in electrochemical cells with electrode
stacks that are sensitive to the distance between electrodes. For
efficiency and lifetime testing in comparison with standard
dimensionally stable anodes (DSA), metal-based diamond
electrodes, such as those based on Nb and recently also titanium,
are used. These are referred to as DiaChem electrodes.
Diachem electrodes are manufactured by HFCVD with
methane and dopant gas (diborane or trimethylboron)
concentrations of up to 3.0 vol% in hydrogen. Typical filament
temperatures are between 2300°C and 2800°C. Substrate
temperatures are between 700 and 925 °C. The films were
deposited at a pressure of 10-150 mbar. Growth rates of 0.2 jum/h
to 2 jLim/h are usually achieved in these systems, with boron
concentrations in the films ranging between 500 and 8000 ppm.

20
2. Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

t%
^^€.
t:

w
I
^—^--SJ

Fig. 2.3. Photograph of polycrystalline film made by the hot

1 filament
CVD method.

2.3. Characterization

The morphology of the films was characterized by scanning

electron microscopy (SEM) with a JEOL JSM-5400 microscope.
The surface morphology produced under the conditions used in
this research consists in general of a highly faceted,
polycrystalline film and uniformly deposited 5-|im diameter
diamond crystallites can be obtained with good reproducibility
from film to film. Fig. 2.3 shows a typical SEM image of a CVD
boron-doped diamond film deposited in this way.
However, some deviations in this faceting were sometimes
observed as a function of both sample position and gas
concentration in the feed gas. For example, in the region more

21
than 2.5 mm from the sample edge, less faceting was sometimes
found.

Fig. 2.3. SEM micrograph of the polycrystalline diamond film

Bachmann et al. have summarized diamond CVD results from

a number of authors. The data were plotted in the form of the
concentrations of carbon, hydrogen and oxygen in a triangular
diagram [l4,15]. It is also clear that crystal growth is highly
affected by the substrate temperature [16-19].
Since CVD diamond is synthesized under conditions in which
graphite synthesis is competitive, in many cases, a non-diamond
component may be incorporated in its amorphous form. The film
quality was confirmed by Raman spectroscopy because it is very
sensitive to graphitic and amorphous carbon (a-C) components-
the Raman scattering intensity of graphite or a-C is about 30
times greater than that of diamond. Raman spectroscopic
measurements were carried out using an Ar^ laser (wavelength =

22
2. Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

514.5 nm) in a Renishaw Raman Imaging Microscope System

(Renishaw System 2000).

1600

1400

1200

1000

800

600

400

20O

800 1000 1200 1400 1600 1800

Raman shift (cm"^)

Fig. 2.4. Typical Raman spectrum of a polycrystalline CVD diamond

film.

A sharp peak was observed at 1332 cm'i, which is

characteristic of diamond and reflects a high degree of
crystallinity, as shown in Fig. 2.4. In addition, a broad peak
centered at approximately 1200 cm'i was observed, which is
usually attributed to either amorphous diamond or extremely
small diamond crystallites [20]. The absence of a peak at -^1500
cm"i indicates that the polycrystalline films are free from sp^
carbon impurities. This type of peak was observed only in poor
quality films. The details of Raman characterization of
diamond thin films are discussed in detail in Chapter 5.

23
References

1. E. Bustarret, E. Gheeraert and K. Watanabe, Phys. Status Solidi

A, 199, 1 (2003) 9.
2. M. Nesdalek and K. Haenan, Semiconduct Semimet, 76 (2003)
325.
3. W. G. Eversole, U.S. Patent, 3030187 and 3030188 (1962)
4. B. V. Derjaguin, B. V. Fedseev, B. V. Spytsyn, D. V. Lukyanovich,
B. V. Ryabov and A. V. Lanentev, J. Cryst. Growth, 2 (1986) 380.
5. J. C. Angus, H. A. Will and W. S. Stanko, J. Appl. Phys., 39 (1968)
2915.
6. B. V. Derjaguin, B. V. Spytsyn, L. L. Builov, A. A. Klochkov, A. E.
Gorodetski and A. V. Smolyaninov, Dokl. Akad. Nauk. SSSR, 231
(1976) 333.
7. S. Matsumoto, Y. Sato, M. Tsutsumi and N. Satake, J. Mater. ScL,
17 (1982) 3106.
8. J. C. Angus, H. B. Martin, U. Landau, Y. E. Estefeeva, B. Miller
and N. Vinokur, New Diamond Front. Carbon Technol, 9 (1999)
175.
9. Diamond Electronic Properties and Application, ed. S.L. Pan, D.
R. Kania, Kluwer Academic Publisher, 1995.
10. M. Kamo, F. Takamura and Y. Sato, Abst of P^ Int. Conf. on the
New Diamond Sci. & Technol, J a p a n New Diamond Forum
(1988).
U . K . Okano, H. Naruki, Y. Akiba, T. Kuraso, M. lida and Y. Hirose,
Jpn. J. Appl. Phys., 27 (1988) L173.
12. H. Notsu, I. Yagi, T. Tatsuma, D.A. Tryk and A. Fujishima, J.

24
2. Preparation and Characterization of Poly crystalline Chemical Vapor Deposited Boron-
doped Diamond Thin Films

Electroanal Chem., 49 (2000) 31.

13. M. Kamo, Y. Sato, S. Matsumoto and N. Setaka, J. Cryst Growth
62 (1983) 642.
14. P. K. Bechamnn, D. Leers and H. Lydtin, Diamond Relat Mater.
1 (1991) 1.
15. T. H. Chein, Y. Wei and Y. Tzeng, Diamond Relat Mater 8 (1999)
1686.
16. Z. Sun, X. Shi, X. Wang, B. K. Tay, H. Yang and Y. Sun, Diamond
Relat Mater, 7 (1998) 939.
17. J. W. Lindsay, J. M. Larson and S. L. Girshick, Diamond Relat.
Mater. 6 (1997) 481.
18. Z. Sun, X. Shi, B.K. Tay, D. Flynn, X. Wang, Z. Zheng and Y. Sun,
J. Cryst Growth 173 (1997) 402.
19. Y. Einaga, G-S Kim, S-G Park and A. Fujishima, Diamond Relat.
Mater. 10 (2001) 306.
20. K. Honda, T. N. Rao, D.A. Tryk, A. Fujishima, M. Watanabe, K.
Yasui and H. Masuda, J. Electrochem. Soc. 147 (2000) 659.

25
3. Electrochemical Effects on Diamond
Surfaces: Wide Potential Window,
Reactivity, Spectroscopy, Doping
Levels and Surface Conductivity

Heidi B. Martin, Sally C. Eaton, Uziel Landau, and John C. Angus

3.1. Introduction

Diamond electrodes have an extremely wide potential window of

water stability, low background currents, chemical and mechanical
stability, resistance to fouling, lack of a surface oxide, and
controllable surface termination. These characteristics have led to
application of diamond electrodes as electrochemical sensors, for
electroanalysis, for electrochemical synthesis, and for anodic
destruction of organic wastes. Boron-doped diamond also can be
used as a transparent, conducting medium for analytical chemistry
and photoelectrochemistry applications. Furthermore, a
fundamental understanding of the origin of the adsorbate-induced
p-type surface conductivity of diamond may lead to devices and
sensor applications.

John C. Angus e-mail: [email protected]

26
3. Electrochemical Effects on Diamond Surfaces: Wide Potential Window, Reactivity,
Spectroscopy, Doping Levels and Surface Conductivity

3.2. Early Studies of Diamond Electrodes

The earliest study of diamond electrodes showed that diamond

implanted with Zn had an overpotential for hydrogen evolution
that was significantly greater than for diamond implanted with Ar
and for glassy carbon [l]. This result indicated that the electrodes
implanted with Zn may have exhibited some of the inherent
electrochemical properties of the diamond rather than of an
amorphous surface layer. However, zinc gives high overpotentials
for hydrogen evolution. Therefore, the zinc itself, if present in
sufficient amount at the surface, may have been responsible for the
observed hydrogen overpotential.
Pleskov et al. made the first extensive study of diamond
electrodes [2]. The electrodes were un-doped, but had sufficient
conductivity, most likely from defects, for electrochemical
measurements. They found a photoresponse at sub-bandgap
wavelengths, which they attributed to excitation of electrons from
mid-gap states to the conduction band. Sakharova et al. made
early impedance studies of diamond electrodes [3].
Patel studied the photoresponse of diamond [4, 5], and Tenne
et al. reported the reduction of nitrate to ammonia on boron-doped
diamond electrodes [6]. Swain and co-workers described the low
capacitance and featureless background current of diamond
electrodes, which are desirable for electroanalytical and sensor
applications [7-11]. Martin and coworkers showed that high
quality diamond electrodes had an extremely wide potential
window of water stability [12-14]. Miller et al. reported on the use
of implanted diamond as an electrode [15], and Carey used

27
diamond electrodes for the anodic destruction of organic wastes
[16].
The early work has been summarized in reviews by Swain [17],
Tenne and LevyClement [18], Swain et al. [19], Angus et al.,
[20],Kobashi [21], and Pleskov [22].

3.3. Properties of Diamond Electrodes

3.3.1. Wide potential window

The surfaces of as-grown chemical vapor deposited diamond
electrodes that have been cooled to room temperature under atomic
hydrogen are terminated with hydrogen. These surfaces are
hydrophobic and not attractive for adsorption. Therefore, electrode
reactions that involve adsorbed intermediates may be strongly
inhibited on diamond. One result, initially attributed to the
hydrogen termination, is a very wide potential range over which
the rate of water electrolysis is negligible [12*14]. Fig. 3.1 displays
voltammograms of hydrogen and oxygen evolution from acid
solution on various types of electrodes. Negligible electrochemical
activity is observed on high quality polycrystalline diamond (or
single crystal, not shown) over a very wide range, extending almost
four volts. Lower quality polycrystalline diamond electrodes, which
contain significant amounts of sp^ carbon have a potential window
similar to that of glassy carbon and highly oriented pyrolytic
graphite. Within the "window" of water stability, other
electrochemical reactions may be observed, which are important for
sensor applications. Also, this wide window allows the generation
of species with oxidation potentials much greater than molecular

28
3. Electrochemical Effects on Diamond Surfaces: Wide Potential Window, Reactivity,
Spectroscopy, Doping Levels and Surface Conductivity

oxygen, for example, the persulfate ion [23]. These data in Fig.
3.1a are typical of diamond electrodes that have been scanned
many times in electrolyte. As discussed further below, including
Section 3.3.4 on surface reactivity, it is likely that some of the
hydrogen termination has been replaced with oxygen containing
groups. This suggests that other factors besides a hydrogen
termination contribute to the wide potential window.

(a) H i ^ Quality Polycrystalline Diamond |(b)Ijow-QiiaIityPoIycrystalline Diamond

j O2 Ewlution I

J,
-2 /
r
HzEwlution
4-^- • -0
-1

Vonse. = - 1 2 5 V
-25
i

ibaseliiie< 0.1 mA/cm

-50^ -50^

Potential v s . SHE(V) Potential v s . SHE(V)

|(c) Platinum (d)HOPG (basal and edge)

25T

?
-4
-25 I
iiMiseiiiie< 1 mA/cm

-sol
Potential v s . SHE(V)

Fig. 3.1. Voltammograms for water electrolysis on four electrodes* a)

high quality polycrystalline diamond; b) low quality polycrystalline
diamond; c) platinum; and d) highly oriented pyrolytic graphite
(HOPG). The supporting electrolyte was 0.5 M H2SO4; scan rate =
200 mV s i . Note the very wide potential window for water stabiHty on
high-quaUty diamond, (a). Electrode potentials are given versus the
standard hydrogen electrode.

29
 Oxygen-terminated, boron-doped diamond has been reported to
have a wider window of water stability and lower background
currents than hydrogenated, boron-doped diamond [24, 25, 26].
Martin et al. [27] observed an irreversible oxidation at +1.4 V (SHE,
0.5M H2SO4) during the first positive scan on a hydrogenated
diamond, which they attributed to oxidation of the surface. For a
0.1 M KH2PO4 electrolyte, oxygen evolution was reported at
approximately +1.6 V vs. SHE for hydrogen-terminated diamond,
+ 1.9 V for electrochemically oxidized diamond, and +2.6 V for
diamond exposed to an oxygen plasma [28].

3.3.2. Nano-crystalline and amorphous materials

Nano-crystalline diamond has a wide potential window of water
stability, similar to that of diamond [29]. The current peak at +1.7
V vs. SHE, often found in voltammograms of polycrystalline
diamond, is absent from these films. Yoo and co-workers reported
that tetrahedral amorphous carbon, ta-C*N, had a chemical
stability similar to that of boron-doped diamond and a wider
potential window for water stability [30]. The ta-C-N electrodes
were more catalytic for electron-transfer reactions than diamond
electrodes, e.g., they exhibited reversible behavior with outer-
sphere couples. These properties are believed to arise from the
presence of sp^ carbon and nitrogen within the amorphous
structure.

3.3.3. Example of diamond as a sensor- detection of plating

additives
The voltammetric detection of typical copper plating additives,
polyalkylene glycol (PG) and disodium (bis(3-sulfopropyl)) disulfide

30
3. Electrochemical Effects on Diamond Surfaces: Wide Potential Window, Reactivity,
Spectroscopy, Doping Levels and Surface Conductivity

(SPS), provides an example of the utility of diamond electrodes for

sensor applications [31]. Figs. 3.2a and 3.2b show cyclic
voltammograms measured on platinum and poly crystalline
diamond of CUSO4/H2SO4 solutions containing PG and SPS,
respectively. The insets of Figs. 3.2a and 3.2b show scans for
platinum and diamond on a 1-mA scale.
On platinum, oxygen evolution occurs at +1.4V (SHE). No
peaks corresponding to oxidation or reduction of the glycol (PG) or
disulfide (SPS) are visible, because the potentials for these
reactions are more positive than the potential for water electrolysis
on platinum, Le., they are outside the "window" of water stability.
However, on diamond, two oxidative peaks are observed for each
additive: +2.05V and +2.4 V (SHE) for PG (Fig. 3.2a), and +1.65 V
and +2.1 V (SHE) for SPS (Fig. 3.2b). The oxygen evolution
observed at +2.4V on diamond does not interfere with detection of
these compounds. Moreover, the relationship between the peak
heights and the additive concentration is linear [31] as shown in
Fig. 3.3.

31
 1mA Diamond
LAJ
!^ Platinum
Diamond
.—--:>• •:
0,5 1.5 2.5 ;• :'

^^ Platinum .' [
1 QJ5 ^ (200mg/L) ; :

I' - 'Wi / .'^ /I

/lOO / ^
'^ 0.05 - /
/^— yOmg/L
i
0.5 1.5 2.5
-0.05 ~ Potential vs. SHE(V)
^ ImA

Platinum
Diamond :
Diamond |
w
0|5 1.5 2-5 ;•
ill

Platinum '•
1 0.015 (80mg/L) ;
80 1
u
u 1
U 0.005 ^ / 40 /

^ •"-•" -••-'
yOmg/L
2.5
-0.005^*^ Poteiitial vs .SHE(V)

Fig. 3.2. Cyclic voltammograms of varying concentrations of (a)

polyalkylene glycol (PG) and (b) disodium (bis(3-sulfopropyl)) disulfide
(SPS) in CUSO4/H2SO4 on platinum and polycrystalline diamond [31].
The insets show scans with a 1-mA full scale. The oxidation peaks of
the two organic compounds are detectable on diamond, but not on
platinum. Note that in Fig. 3.2a the concentrations of PG are 0, 20, 50,
100, 200 and 400 mg LK

32
3. Electrochemical Effects on Diamond Surfaces: Wide Potential Window, Reactivity,
Spectroscopy, Doping Levels and Surface Conductivity

0.20 T

R^ = 0.988

Peak Currents Measured for

Oxidation Peak at E„ = +2.1 V
J I I 1 I I L_l |_B 1 1 1 1

100 200 300 400 500

[Polyalkylene Glycol] (mg/L)

Fig. 3.3. Oxidation peak currents for polyalkylene glycol at

Ep=+2.1 V v s . SHE (from Fig. 3.2) increase linearly with increasing
glycol concentration [31].

3.3.4. Reactivity
Diamond has remarkable chemical stability compared to other
electrode materials. Li et al. [32] liberated Li from Li+ in a
polymeric electrolyte on a diamond cathode. No intercalation of
lithium or any reactivity with the diamond was found. Diamond
electrodes can easily oxidize cyanide under conditions where
traditional anodes such as Pb, Ir02, and Ru02 fail [33].
Diamond electrodes are, however, not completely inert.
Chemically bound oxygen appears on a diamond surface after
anodic polarization or oxygen plasma treatment, and the electrode
surface changes from hydrophobic to hydrophilic [2, 14, 27, 28, 34,
35, 36]. This is observed on both poly crystalline and single crystal

33
diamond. However, cyclic voltammetry shows the presence of a
redox couple at +1.7 V vs. SHE on polycrystalline diamond that
does not appear on single crystal electrodes [27], which implies
some grain boundary reactivity not found on single crystal diamond.
Electrodes with significant sp^ carbon in the grain boundaries are
less stable under anodic polarization and eventually disintegrate.
Fluorination [37, 27] or anodic treatments in basic solution [38, 25]
have been shown to either passivate or etch the sp^ carbon in the
grain boundaries, as evidenced by the absence of the redox couple
at+1.7 V (SHE).

3.3.5. Transparency
Diamond's relative transparency, even when doped, permits it to be
used as a transparent electrode. Martin and Morrison [39] have
exploited this phenomenon to detect changes on the diamond
surface during polarization. They found evidence that OH
functional groups appeared on the diamond surface, primarily ( i l l )
facets, during anodic polarization. In Fig. 3.4, one can see that the
3240 cm 1 0-H and 1100 cm ^ C"0 stretch peaks increase with
increasing polarization. Notsu et al. [40], using a chemical method,
independently observed hydroxyl groups on ( i l l ) films, through
preferential coupling to the -OH. Zak et al. [41] have also reported
transparent diamond electrodes for electroanalysis-
ferri/ferrocyanide and methyl viologen were electrooxidized in a
thin layer transmission cell with a free-standing diamond disk as
the transparent electrode.

34
3. Electrochemical Effects on Diamond Surfaces: Wide Potential Window, Reactivity,
Spectroscopy, Doping Levels and Surface Conductivity

IJ

o
>
o
o 1-

1.0 V-forward
995- 2.0 V - forward
3.0 V - forward
1.5 V - reverse
QQ—
.W 1 \ \ 1 \
5000 4000 3000 2000 1000
Wavenumber (cm-1)
Fig. 3.4. Infrared spectra taken during step-wise polarization of a
diamond electrode at various potentials [39]. The feature at 3240 cm'^
is assigned to O'H stretching while the feature at 1100 cm'i is
assigned to C-0 stretch. Both features increase with increased
polarization.

3.4. Semiconducting Diamond Electrodes

3 . 4 . 1 . D o p i n g of d i a m o n d
Boron-doped diamond has been widely studied, and some of the
properties of relevance to electrochemistry have been reviewed [20,
42, 43]. Substitutional boron at low concentrations gives an
acceptor level at 0.37 eV above the valence band [44]. At very high
concentrations of boron (> lO^o cm'^), a dopant band is formed [44-
49]. The resistivity ranges from about 10^ Q cm at a boron
concentration of lO^^ cm'^ to tenths and thousandths of an Q cm for
boron concentrations of the order of lO^i cm'^. At high boron levels,

35
the potential window of water stability decreases and the
crystalline quality decreases [50].
High levels of boron incorporation are desired for applications
where low resistivity is required. The boron incorporation on ( i l l )
faces is approximately ten times greater than on (lOO) faces [51,
52]. Also, higher boron levels are achieved in hot-filament reactors
than in microwave plasma reactors [53]. The presence of oxygen in
the reaction gas greatly reduces the concentration of boron
incorporated in the diamond, presumably because of the formation
of stable oxides of boron [54-57]. These results on boron
incorporation are summarized in the review by Angus et al. [20].
Nitrogen and phosphorus give deep donor levels in diamond,
1.6 eV and 0.6 eV below the conduction band, respectively. Sulfur
has been reported to give n-type conductivity [58, 59]. However,
other work indicated that the samples contained boron and were p-
type [60]. Eaton et al. found that sulfur incorporation in diamond
was facilitated by the presence of boron [61-63]. They obtained
diamond with n-type conductivity by co-doping with sulfur and
small quantities of boron; however, the sulfur was concentrated in
the near surface region [63]. Density functional calculations by
Albu et al. [64] predict that substitutional S and BS centers are
deep donors, each with a level about 1.5 eV below the conduction
band, which is too deep to provide significant thermal excitation at
room temperature. However, they also found more complex B/S/H
centers that produced midgap states that might lead to impurity
band conduction at sufficiently high concentration. Eaton et al
[65] performed electrochemical measurements on the B/S co-doped
n-type diamond. Mott-Schottky measurements showed a positive

36
Exploring the Variety of Random
Documents with Different Content
of consciousness that came from time to time,
although a new symptom had appeared in the
extreme restlessness that alternated with the
lethargy.
For six weeks hope came and went, everything
being done that love could devise or devotion carry
out. In addition to the two constant companions,
there were two trained nurses: and the dear patient,
in the quiet intervals, was her sweetest self; so
careful about giving trouble, and so courteous in her
acknowledgment of service rendered, so grieved that
the nurses should be kept up at night, and so
anxious that Miss Millner and Miss Edwards should
know how much she felt their kind attention.
Miss Edwards gives some interesting details of
these last months after the return home from this
last holiday, when, after a few weeks of care and
nursing, she had seemed better than at any time
during the year:—

“Three weeks of peaceful, quiet enjoyment followed this

illness, during which Miss Buss received many of her friends
at her own house, and was further made happy by a visit
from her old and intimate friend, Mrs. Hodgson, who has
since written: ‘I am very thankful that I had such a sweet,
happy time with my friend before the last illness came, and
when she could in a measure enjoy life.’
 “During this period of improved health Miss Buss paid her
last three visits to the school she loved so dearly, visits that
will not soon be forgotten by those who then saw her. On
October 31st she was present in the evening at the ‘old
pupils’’ meeting, and on November 2nd, during part of the
school concert, and, with her usual sympathetic thought of
others, sent on each occasion for several of the music
teachers and others of the staff to sit by her in turn and
exchange a few words.
“The last occasion on which our dear head-mistress was at
Sandall Road was on November 7th, when she distributed
the holiday prizes, making kindly inquiries, as each girl whom
she knew came before her, for parents and brothers and
sisters at home, and taking special notice of the little ones,
for whom she had brought a large packet of sweets.
“Before this illness came on she had with her own hands
arranged all her Christmas gifts and ordered her Christmas
cards, received by many of her friends on that sad Christmas
Day. There were also some packets addressed by herself of
mementoes to friends, all the more precious for this evidence
of thoughtful foresight.
“On Saturday, November 10th, friends came to lunch, and
Miss Buss was well enough to enjoy their society, and show
particular interest in the children, finding games and other
amusement for them.
“On this day also she had a visit from an old pupil—and
colleague—who brought her little baby-girl, asking
permission to call her Frances Mary, a request which greatly
touched Miss Buss. Constantly during her illness she spoke of
her ‘little namesake baby,’ who once, at the dear invalid’s
special wish, was brought to see her.
“On November 11th Miss Buss attended the short morning
service at the church of St. Mary the Virgin, almost next door
 to Myra Lodge.
“On Monday evening she was able to be with the girls at
No. 89, enjoying, as she always did, to see them happy in
playing games.
“The next day two old pupils took tea with her, and for the
Wednesday a luncheon-party of some of the clergy and
workers of Holy Trinity had been arranged. But this, by the
doctor’s orders, had to be postponed.”

On the Thursday before the end there was a

return of consciousness for some hours, with full
recognition of her nephew, the Rev. Charles Caron
Buss, the “Charlie boy” of olden days, whom she now
questioned tenderly about his little curly-headed
Kenneth, her latest delight. She also recognized and
talked with Mrs. Alfred Buss. Then came her “own
boy,” the Rev. Francis F. Buss, and she was able to
follow the Service for the Visitation of the Sick, and
to join once more in the Veni Creator, and then, for
the last time, in the words of the Collect, so often on
her lips, to seek from the “Fountain of all Wisdom
those things which for our unworthiness we dare not,
and for our blindness we cannot, ask”—a prayer so
meet for one who had walked from earliest days so
humbly with her God—a prayer so soon to be
answered by the revelation of “the things prepared
for them that love.”
 With this last self-surrender she let go her hold on
earth, sinking again into a state of coma that grew
deeper and deeper till it merged into the sleep of
death. It lasted for three whole days longer, during
which her family and a few intimate friends were
unremitting in their visits, though there was nothing
to be done but take a sad look at the dear face, and
go away with the terrible sense of change, as they
thought of that still form, those closed eyes, those
unanswering lips from which came now only that
slow laboured breathing, and remembered their
friend as they had always known her before, so alert,
so alive to every touch, so quick of response to the
faintest appeal. The only break in this long stillness
came in the hymns which from time to time were
sung softly by the watchers at the bedside, in the
hope that those familiar sounds might penetrate,
beneath the silence.
All Sunday night the family remained in
expectation—almost in hope—of the release which
seemed so near, waiting as they that watch for the
morning. Christmas Eve dawned, and, as the day
advanced to high noon, the heavy breathing grew
more and more quiet, till at length came perfect
peace, and the watchers knew that their beloved had
passed from death to life.
“For fifty years with dauntless heart
Step after step she won her way,
Through times of cloud, and barren praise,
Up to the well-earned golden days
Of proud success, and prouder fame;
Where no high thought of self had part,
No poor ambition of display,
To dim the lustre of her name.

“So, far and wide, o’er mead and lea,

Was sown the seed; and many a waste
Broke into blossom; fields grew white
To harvest that she lived to see,
Though not the fuller fruit to taste
(Which ages yet to come shall reap)
Ere fell the shadow of the night,
And, dauntless still, she sank to sleep.

“To busy hands and weary brain

Thus comes at last the dawn of peace,
Rest after noble toil, in light
Beyond the shadows, infinite;
Yea, life in Him who once again
By death for ever lives: release
From bonds to freedom. None may tell
Her bliss, but surely ‘SHE SLEEPS WELL.’”
(Rev. B. G. Johns.)
 CHAPTER VI.

“AND HER WORKS DO FOLLOW HER.”

“Give her of the fruit of her hands: and let her own works
praise her in the gates.”—Prov. xxxi. 31.

“Of feeble knees the strengthener,

The stay of timid hearts,
Does all her might go out with her
Who now to rest departs?
Nay, for the children of her love,
To their full stature grown,
Must learn amid their tears to prove
How they can go alone.”
Emily Hickey.

Fifty years of work! Of work that, had she been other

than she was, might have been mere thankless
drudgery; of work that, being what she was, remains
a living influence, spreading, in ever-widening circles,
to distances beyond compute. Fifty years of love,
poured out from a heart often disappointed, but
never embittered; often left unfilled, but never found
empty; often strained to utmost tension, but never
relaxing its high energy. Being as she was, refreshed
by the living water, sustained by the bread of life, the
strength was hers that knows neither drought nor
famine.
For more than forty years she had worshipped in
the same church—Holy Trinity—built by her friend
the Rev. David Laing, and afterwards held by her
friends, the Rev. E. Spooner, the Rev. Charles Lee,
and Dr. Cutts.
To this altar she came, through all her working
time, to renew the strength in which her work was
done as “Christ’s faithful soldier and servant to her
life’s end.” And here, when that end came, the last
gleams of the dying year fell on the white blossoms
that hid all that was mortal of that brave spirit, while
the vast crowd knelt to give thanks for a life which
had made all life so much the more worth living to
themselves and to all women who should come after
them.
“The good die never!” There can be no end to this
high influence that for the half-century past has gone
out, carrying with it all that is true, all that is pure,
all that is lovely. It must still go on in the centuries to
come in added power, since
 “Good, the more
Communicated, more abundant grows.”

And yet, do we not too sadly feel that the end has
come for us, who will not again, while we tarry here,
look on that kind face, or feel the clasp of that hand
that seemed strength itself? We rejoice in the joy of
her immortality—here and hereafter—but for us, here
and now, there is the suffering of this present time,
which is “not joyous, but grievous.”
How much she did! She worked till the last; till
those magnificent energies, which seemed
inexhaustible, were at length worn out.
She “died in harness,” and we must not grudge her
what she would have chosen. But yet, how we wish
it might have been otherwise! That she might have
rested in time, to have saved herself to be with us a
little longer, an inspiration and strength to all; “a
great moral force in the educational world;” an
example to all teachers, as well as to her own staff
and her own pupils; a joy to the friends who loved
her; and to her own nearest and dearest——? But
here we pause and are silent before her brother’s
words: “I cannot speak of what she was—and what
her memory will be—to her nearer relatives, and
especially to us, her brothers.”
 The details of the service in Holy Trinity and the
concluding ceremony in the quiet churchyard at
Theydon Bois, near her cottage at Epping, on the
edge of the Forest, are given by eye-witnesses,
happy in being permitted to be there to see and hear
for themselves.
Never, it seemed to me then, could physical
disability have pressed more heavily than during that
week—from Christmas Eve to New Year’s Eve—when,
although no farther distant than St. Leonard’s, I had
to submit to be absent, while so many friends were
doing honour to her whom we all loved and
mourned.
The events of the three days, so full of emotion,
could not be better told than as they are given in the
“Memorials” compiled in the beginning of the year, by
her old pupils—afterwards colleagues—Miss Edith
Aitken, Mrs. W. K. Hill (Eleanor M. Childs), and Miss
Sara A. Burstall, who record the scenes at Holy
Trinity, at Theydon Bois, and on the first day of the
re-opening of the schools.

THROUGH THE GRAVE AND GATE OF DEATH.

“It is the will of God that even to the most vigorous and
faithful of His servants there shall come, sooner or later,
weakness and decay of strength. There is nothing more
simply sorrowful than this, and yet it is an integral part of the
providence of the world. To the most fortunate and gifted
life, full of great opportunities, to which the character and
personality were equal, to a life blessed with health and
power and love and success and a large measure of
happiness, even to such a life comes old age, with its train of
disappointment and feebleness. It is true that the waning of
a noble life is often marked by a sweetening and mellowing
of character, which is in itself a triumph and a glory; but still
the growing earthly feebleness cannot be forgotten, and it is
a sad thing to watch the face change, and to hear the voice
ever weaker and the step ever feebler, and to know that
strength is gone and will come back no more in this life. The
grasshopper has become a burden; the night is at hand.
“During the last year we have shared in such growing
sorrow, as we have watched the struggle of an eager and
hopeful spirit against increasing physical pain and weakness.
We have hoped against hope, for the spirit was still so
willing, but the foreboding was always there, and in the last
dark days of the old year the end came, irrevocably and, as
it seemed, almost suddenly. No more alternations, no more
struggles; all was over.
“What an oppression of loss and pain seemed to brood
over us as we waited through that dark winter’s morning in
the dim church full of mourning figures! Crowds of people
witnessed to the wide-reaching influence of the life of which
we were thinking. The solemn dignity of the occasion, as we
caught a glimpse of one and then of another who had come,
each from his or her important place and work, to take a part
in this last ceremony of respect, recalled the importance of
the life-work now over. Especially did the sight of such a
veteran of the struggle as Miss Emily Davies bring to mind
touching memories of the fight for an ideal waged in the
beginning against great odds. Such had been this our leader
—an important force in the world, a mind of originating
insight, who had modified her age for good. But now all was
over. We had had the privilege of being with her, but we
should have it no more. Our lives for the future were to be
poorer and smaller.
“The tolling bell seemed to beat out such thoughts as we
waited. But these more general regrets are changed to the
acuter stab of personal grief, as the coffin is carried in and
passes us close. It is to this that the loved presence has
come, and even this is for the last time. A hundred personal
details come back—her dress, her favourite colours, her
smile, the sound of her voice. Thus and thus we knew her—
and shall know her no more.
“‘The best is yet to be.’ We believe it, but we loved her as
she was.
“It is hard to control our voices, but we are still her army.
It behoves us to show that we can respond to the word of
command, and so we take our part in the service, and all
goes on in its appointed order to the end. The coffin is
carried out, and we disperse on our further journey, sad and
dreary, down to Theydon Bois. Our minds are filled by
thoughts of the past and of the future. To many of us the
best part of our lives is associated with her. To how many
has she not been a generous and inspiring friend, who
brought out all our best by her very belief in it? How are we
to go on without her? And how drearily ashamed we feel of
our worst, which we can never now amend before her.
“It pleased God to let our final farewell be very beautiful.
The churchyard at Theydon lies on the slope of a hill, and
the grave is at the northern side of the low, red brick,
country church. The short winter day was drawing to its
close already, and the western sky was glowing with glorious
red and gold. The procession was marshalled in the road
below, and the white-robed clergy came down to meet us
from out of the sunset light, as it seemed. Our hymns of rest
and triumph felt right and fitting then, as we thought of her
and not of ourselves. She had fought a good fight, and had
finished her course. The country fields lay bare about us, and
the branches of the trees, interlacing themselves between us
and the evening sky, were leafless. But everything was
touched with a most tender and beautiful light, as large, soft
snow-flakes floated gently down on the violets and white
spring flowers with which we covered her. And so we left
her.”

“‘The souls of the righteous are in the hand of God, and

there shall no torment touch them;
In the sight of the unwise they seemed to die, and their
departure is taken for misery,
And their going from us to be utter destruction. But they
are in peace,
For though they be punished in the sight of men, yet is
their hope full of immortality.’”
Edith Aitken.

THE FUNERAL SERVICE.

“On the last day of the old year Holy Trinity Church,
Kentish Town, was filled to overflowing with those who had
met to pay their last tribute to her who had passed away
from among us. The greater number of the mourners
consisted, as was natural, of past and present pupils of the
North London Collegiate and Camden Schools, but in addition
there were representatives of all branches of education in
the widest sense of the word. Among these we may mention
Rev. T. W. Sharpe (H.M. Chief Inspector of Schools),
Professor Hales (King’s College), Prebendary Whittington,
Rev. Brooke Lambert, Rev. H. L. Paget, General Moberly
(Vice-Chairman of the London School Board), Mr. Latham,
Q.C. (representing the Clothworkers’ Company), Mr. Alfred
Bevan (representing the Brewers’ Company), Mr. Elliott and
Mr. Danson (Governors), Mr. Storr (Merchant Taylors’ School),
Mr. Hinton (Haberdashers’ School, Hoxton), Dr. Evershed, Dr.
J. Collins, Mr. Percy Bunting, Mr. Courthope Bowen, Mr. W. C.
Bell (Treasurer of the Cambridge Training College), Miss
Agnes Ward, Miss Hadland, Mrs. W. Burbury (Governor), Miss
Prance (Governor), Miss Day (Greycoat School), Miss
Andrews (Maida Vale High School), Miss Armstrong (Dame
Alice Owen School), Miss Penrose (Bedford College), the
Misses Metcalfe (Hendon), Miss Huckwell (Leamington), Miss
Green (Blackburn) and Mrs. Mary Davies.
“Long before the time appointed for the service—10 a.m.—
every seat in the church, which is said to hold about two
thousand, was filled, while many people were standing in the
aisles. As the coffin was brought in at the south door, the
door by which Miss Buss had entered Sunday after Sunday
from the time the church was built, the whole congregation
rose to its feet, and remained standing until the mournful
procession reached the chancel. It was impossible, even
then, to realize that we should never again on earth see that
familiar face, never again hear the kindly words that so often
cheered and encouraged us in our darkest hours, making us
feel that, after all, life was worth living, and that each one of
us had her special work to do.
“All the arrangements had been most carefully planned
before. The chancel, with the seats behind, was reserved for
the family and immediate mourners, Governors of the
Schools and representatives sat in the front seats, teachers
and present pupils of the North London, all of whom carried
white flowers, in the body of the church. The west gallery
was appropriated to the Camden School, while the rest of
the gallery and the side aisles were filled with old pupils and
friends. The pall-bearers were:—
 Professor Hill.
(Of University College, London.)

Dr. Garnett.
(Educational Adviser of the Technical Education Committee of
the London County Council.)

Mrs. Bryant.
(Vice-Mistress of the North London Collegiate School.)

Miss Lawford.
(Head-Mistress of the Camden School.)

Miss Hughes.
(Head of the Cambridge Training College.)

Miss Jones.
(Head-Mistress of Notting Hill High School and President of
the Head Mistresses’ Association.)

Miss Emily Davies.

(One of the Founders of Girton College.)

Miss Beale.
(Head of the Ladies’ College, Cheltenham.)

Dr. Wormell.
(Head-Master of the Central Foundation Schools, Cowper
Street, representing the College of Preceptors.)

Dr. Fitch.
(Member of the Senate of the University of London,
representing the Teachers’ Guild.)

“Mrs. Green was at the organ, and the girls’ choir led the
singing, which consisted of Psalm xxxix., the ‘Nunc Dimittis,’
and the hymns ‘The saints of God, their conflict passed,’
‘Peace, perfect peace, in this dark world of sin,’ and ‘Now the
labourer’s task is o’er.’
“After the service, which was conducted by the Vicar (the
Rev. Dr. Cutts), Canon Browne, whose work in connection
with the Cambridge Local Examinations brought him for so
many years into such close contact with Miss Buss, delivered
an address from the chancel steps. He said the last rites
were often performed over those who were too young to
have shown promise; over those who had shown promise,
and were cut off, as it seemed, prematurely; over those who
had lived longer, and had had no aim, done no work in life;
over those who had had noble aims, and had been
disappointed, or who, having seen the fulfilment of their
aims, had outlived their friends, and died silent and alone.
How exactly the opposite of all this was the record of
Frances Mary Buss! She had great aims, she had seen a
noble work perfectly done, she was surrounded to the last by
affectionate friends. It was not too much to say that she was
one of the most prominent actors in that which had changed
the face of a large area of human life. There were many
present who had played a large part in it, but he could not
name the living. Miss Anne Clough and Miss Buss were, of
those who had passed away, those who had developed the
best of woman’s nature, the latent power and charm of that
intellect which was so subtle in its intuition and so swift in its
spring. Miss Buss had reduced the wear and tear of effort by
the improvement of method, and had changed that which
had been dull and flat and painful into brightness and
interest. Thousands of girls’ lives had been made happier,
hundreds of women were now doing congenial woman’s
work through her means. It was difficult to believe that it
had all grown from nothing in thirty years. It was not with
her as with many—that others had laboured, and she had
entered into their labours; she was herself the pioneer, and
herself had crowned the work. It had not been done from
policy; it had all come from love and sympathy, combined
with that practical intuition which always lays its finger on
the important point. Now her task was o’er, that faithful
labourer, under whom a wilderness had grown into a garden,
the garden had blossomed into flowers so fair, had borne
fruit so sweet. It was the last day of the year, the eve of a
New Year. The Church’s lessons brought before them that
beautiful chapter of the Revelation which described the new
heavens and the new earth. Miss Buss’ quiet and decided
religious character enabled them to enter without hesitation
on that branch of thought. Her religious character shone
naturally throughout her educational work. They read of the
garnishing of heaven with precious stones of various hues
and many names, not there because of this hue or that, of
this characteristic or the other, but because they were
precious stones. In all reverent faith they followed in
imagination the placing of their friend, now lost here, among
the precious stones in heaven, and they might pray that of
themselves it might be true that she was but gone before.
“The second part of the service was performed in the little
churchyard of Theydon Bois, near ‘Boscombe.’ The journey
seemed to be made doubly sad by the remembrance of the
many delightful holidays we had spent at ‘The Cottage,’ and
by all its associations; and yet we felt that we would rather
she were laid to rest there, in the open country, than in a
crowded London cemetery. ‘After life’s fitful fever she sleeps
well.’
“The day was piercingly cold, in spite of the bright
sunshine, and the ground was covered with snow. About six
hundred went down to Theydon Bois by a special train, and
the long procession was formed at the foot of the hill on
which the church stands. Mr. Garrod, Secretary of the
Teachers’ Guild, Mr. Foster Watson, Master of Method at
Aberystwith College, Mr. Pinches, Treasurer of the College of
Preceptors, and Mr. W. K. Hill, Head-Master of the Kentish
Town School, acted as marshals. At two o’clock, the hearse
and carriages with the chief mourners reached the spot, and
the long train of mourners, headed by the clergy, the Rev. C.
E. Campbell, Vicar of Theydon Bois, Canon Barker, and
Canon Browne, moved slowly up the hill. Immediately behind
the clergy came the girls’ choir, singing ‘How bright the
glorious spirits shine.’ The voices, subdued as they were,
owing to the great length of the procession, had—if one may
so express it—a wonderfully spiritual effect. The churchyard
was quite filled with the mourners, and after the actual
service was finished, Canon Barker delivered a short address
to those assembled round the open grave on the life-work
and lessons taught by Miss Buss, whose name, he said,
would be connected with the commencement of the higher
education of women for many years to come. He dwelt on
the zeal and ability displayed by the deceased in founding
the great school in Camden Town, and the most important
educational testimony she had given before the Schools
Commission. Miss Buss also established the Head-mistresses’
Association and the Teachers’ Guild, and her schools were
the models of those of the Girls’ Public Day School Company.
The effect and success of her work was seen at Girton and
Newnham Colleges, and at the London University, and he
mentioned the fact that at one time at least two-thirds of the
girls at Girton were from Miss Buss’ own school. The chief
point in regard to her character was her remarkable
personality and indomitable strength. Her simplicity and
singleness of heart were without a taint of personal
ambition. He dilated on her great power of assimilating new
ideas, and said the influence of her will was extraordinary.
Her name would live for years, and the women not only of
this country, but of every other, owed her a debt of gratitude
for the noble work she had accomplished. He touched upon
her deep religious character, manifested so clearly in her
quiet advice and consolation to the girls who came to her in
 any worry or trouble, and finally he said it was a blessing to
any one to be able to see, as Miss Buss had done, her life’s
work crowned with success before she departed.
“In compliance with the expressed wish of the family,
comparatively few wreaths were sent, but these were quite
as many as could well be dealt with. In addition to those
from members of the family, the teachers of the North
London Collegiate School sent a wreath of laurel, the
Camden School teachers a wreath, Miss Ridley (a Governor
of the school from its early days) and Miss J. T. Ridley a
wreath, Myra Lodge an anchor of violets, while the pupils
festooned and decorated the hearse. Most of those present
carried flowers, which they threw into the ivy-lined grave.
“For the greater part of the service large flakes of snow
had been slowly falling. The day will ever remain in our
hearts. Though one of deep sadness, yet there was withal a
feeling of gratitude that we, too, had known her, and of pride
that we were Miss Buss’ girls.
“Eleanor M. Hill.”

It is impossible to do more than merely indicate

the feeling caused by the death of Frances Mary
Buss, as evidenced in the piles of letters addressed
to her family, and to Mrs. Bryant and members of the
staff, by leaders in the educational world, as well as
by pupils, past and present, and by friends from
every part of the globe. The extracts already given
will serve to represent this deep and widespread
sense of loss, and to show in how many hearts her
memory will live on.
 Of outward and visible memorials there are several
still in progress. One only is as yet completed, a
window given by relatives and friends to Holy Trinity
Church, where, on October 3, a special dedicatory
service was held. The subject is St. Scholastica, the
devoted sister of St. Benedict who founded Monte
Cassino, the first monastery of the Western Church.
St. Scholastica is said to have helped largely in the
revival of religion and learning that marked the sixth
century. She became the Head of the first community
of nuns, and it is in this character that she is
represented in the upper part of the window. In the
lower part she is seated, with one of her young
novices at her knee, in keeping with her name, and
with the work of the great teacher thus
commemorated, whose likeness is plainly
recognizable in the features of the saint. Above the
head of the upper figure runs a scroll with the words,
“I know thy works, and charity, and service, and
faith” (Rev. ii. 19). The inscription below is, “In loving
memory of Frances Mary Buss, for forty-five years a
communicant of this Church.”
The memorial window in the Clothworkers’ Hall,
Sandall Road, which is to be the gift of the Company,
is still in progress. The design represents four typical
women from sacred history, all peculiarly appropriate
—
 I. Deborah, “a mother in Israel” (Judg. v. 7).
II. Huldah, “the prophetess,” with whom “many
communed” (2 Kings xxii. 14).
III. Mary, who “chose the better part” (Luke x. 42).
IV. Phœbe, “a servant of the Church, and a succourer of
many” (Rom. xvi. 1).

A portrait is introduced into the design.

In the Camden School there is to be a marble
bust, the gift of the same generous donors, who
have already done so much to beautify the schools.
But the memorial which would most have pleased
her whose name it will bear is in the Travelling
Scholarships, to which the public subscriptions are to
be devoted. In keeping with the large-heartedness
which knew no bounds, the benefit of these
Scholarships will not be confined to the two schools
of which she was the founder. It is hoped that many
a worn and jaded teacher may thus derive from
foreign travel the rest and refreshment which so
often sent Miss Buss herself back to work with
renewed vigour; and it can scarcely be doubted that
in extent these Scholarships will prove worthy of one
who so largely gave to others.
The account given by Miss Burstall of the re-
opening of the school after the great change that
had come upon it is full of interest—

“The opening of school on the first day of term was a

strange, but inspiring and impressive, ceremony, which none
of those present are likely to forget. The dark ranks of the
girls, as they stood for prayers, the black dresses of the
teachers, the laurel wreath hung above our dear Founder’s
portrait, the empty great chair, which would never be filled
again by her we had seen there so often—all told the story
which the funeral hymns[21] sung before and after prayers
reiterated. When the short, very short, service was
concluded, the Rev. A. J. Buss came forward, and first, on
behalf of the family, thanked the staff for their work (a very
labour of love indeed) in organizing the funeral
arrangements, and the girls for their singing on the sad
occasion. He then, as Clerk to the Governors, went on to say
that the Governors had been unable, owing to the shortness
of the time that had elapsed, to make any final arrangement,
but that they had asked Mrs. Bryant to take the post of
acting Head-mistress during the term.
“Mrs. Bryant, after saying a few words in response to Mr.
Buss, gave a short address, expressing (as she said) the
thoughts and memories that rose to the surface in trying to
realize the greatness of the leader who had passed from
among us. Sympathy, absolute devotion of self, extraordinary
energy of will, marvellous charity—these one thought of as
they had been shown year after year in counsel, in delight in
other’s pleasures, in carrying ideas into action, in patience
and help to inferior workers, in honour and appreciation to
talent, in raising the weak, in strengthening the strong.
“The thrill of emotion, of loyalty, of sorrow, and of hope,
which passed through the hearts of so many of us as she
spoke, is too personal, too sacred for expression. It was a
relief when music, that divine art which begins where words
 end, came to speak regret and aspiration, as the solemn
chords of the Dead March in ‘Saul’ flowed from the organ.
Just at this moment, a little after 9.30 a.m., a winter
thunderstorm rolled up. The light grew fainter, the wind
sounded round the building; still the music pealed on as the
darkness gathered, rising stronger and fuller in its confidence
of triumph over death, when, just at the climax of the
melody, a flash of lightning blazed for an instant like an
answering fire from the heavenly world. It was a strange
coincidence, but it was not the first time that Nature had
seemed to sympathize with our grief and with our
consolation. The flowers and the winter sunshine of New
Year’s Eve, the softly-falling benediction of the snow in the
churchyard at Theydon—these had their meaning. So, too,
had the symbol of power, of energy, of light in darkness,
when the New Year began with its new work and its new, yet
old, inspiration.”

21. “The saints of God, their conflict passed,” and “Peace, perfect
peace.”

The music ceased, and all stood for a moment in

silence, till, as Miss Fawcett tells us—

“Mrs. Bryant said very quietly, ‘The classes will now pass to
their own rooms as usual!’ and, as we obeyed, the clouds
cleared away, and the place was soon flooded with brilliant
sunshine. ‘Le roi est mort: vive le roi!’ was the thought in all
minds. But our new Head had taken her stand on the old
order of things, and there is sweetness in our sadness.”
 Owing to some technicalities which could not be
set aside, the post of Head-mistress was still not
filled officially either on the Foundation Day or Prize
Day, June 27, 1895, and these may therefore be
counted as the last days of the old régime, the
beloved Founder still holding supreme rule, through
the self-effacing loyalty with which her successor did
honour to the cherished memory.[22]
22. In a paper found in Miss Buss’ desk there is gratifying proof of
the satisfaction it would have given her to know of the choice
of her successor—
“I know Mrs. Bryant well, and think her the most competent
woman in the whole range of my acquaintance to take up my
work after me. She is bright, accomplished, energetic, and
earnest. She is amiable and loving, and, above all, has vital
force. She has, indeed, ‘a healthy mind in a healthy body.’
Pages of writing could not express more strongly my conviction
that she is the one woman who would and could carry on the
school in the same spirit as it is carried on now. Her fellow-
workers would also be loyal to her, and she would be
considerate about them.
(Signed) “Frances Mary Buss.
“Myra Lodge, Feb. 3, 1878.”

On Foundation Day (April 4)—henceforth to be

known as Founder’s Day—the sense of loss was
manifest in the black dresses of the staff, and in the
absence of the usual daffodils with which the Hall
had been gay in past times. The needlework was
shown as usual, but in place of the entertainment of
other years, there was an organ recital, followed by a
selection of sacred music, ending with the hymn, so
deeply impressive to all there, “The saints of God,
their conflict passed.”
On the Prize Day (June 27) there was a special
appropriateness in the fact that in Professor Jebb of
Cambridge, who occupied the chair, there should
have been so distinguished a representative of the
University which had been so much to one who had
laboured to open for others the way thither which
she could not herself follow.
In the presence of Lady Frederick Cavendish, who
gave the prizes on this last day, there was also a very
special fitness, not only as a very active member of
the Council of the Girls’ Public Day Schools Company
—a work made possible in the beginning by Miss
Buss’ success in her schools—but still more as the
daughter of Lord Lyttelton, one of the earliest friends
to the higher education of girls in general, and, in
particular, to the North London Collegiate and
Camden Schools for girls.
The day was further marked as the close of the
first great period of the School’s history by the
absence, not only of the Head herself, but of two of
her foremost helpers—the Bishop of Winchester and
Mr. Elliott—the one suffering from the illness so soon
to prove fatal, and the other from sudden
bereavement. So far back as 1879 Miss Buss, in
regretting the absence on the opening of the new
Hall of the Rev. Charles Lee, had thus written of
these three friends—

“For years past Mr. Lee was the one person who was
guide, philosopher, and friend; who gave up his time, and
who, with Mr. Elliott and Mr. Thorold, met constantly in
Camden Street, looked after Myra Lodge as well as 202,
worked up the law questions (Mr. Elliott has always given his
law knowledge to me and to the movement from the
beginning), and in fact worked hard when friends were few
and success was apparently hopeless.”

Mr. Lee’s removal from London deprived Miss Buss

of his valuable help, but for fifteen years longer Dr.
Thorold and Mr. Elliott were by her side in any time
of need, and their kind and genial speeches had
come to be an essential part of Prize Day rejoicing.
And so the old order changes once again. But, no
longer looking sadly backward, we may turn
hopefully to the future, as past and present are
united in the heartfelt tribute to the Founder with
which her successor takes up the work of the school.

“Last year I stood behind her in this place and read the
Prize Day report, which was her report, for her. To-day I am
proud to be her deputy once again and glad, for this day at
least, of the circumstances which have determined that as
yet no one speaks in her place as more than a deputy.
“The thought of our School’s past—the pride in it, the
regret for it as past—must be specially with us all to-day. For
the first time in forty-five years we meet together for our
yearly distribution of prizes without the gracious presence of
the Founder, a presence so familiar, that cannot be replaced.
A great teacher, a wise administrator, a strong and
sympathetic leader, she held a place almost as unique in the
educational world as the history of the schools she founded.
Nevertheless, the loss to us in this school is deepest, widest,
most intimate. To those who have been her colleagues, the
sense of it is ever present, in all the details of work, and
affecting all the relations of friendship.
“Noble work like hers remains in effect for all time, and
great inspirations are immortal, passing on from mind to
mind. The neighbourhood knows, and will long know, our
building as ‘Miss Buss’ School,’ and our traditions have
already lived too long to lose the stamp of the character that
moulded them. To guard them with care, to act on them with
zeal, will be the pleasure and duty of every North London
girl.
“It is, I believe, hardly necessary, but I would like, before
concluding, to remind the pupils of the thanks that are due
to the teachers for their never-failing interest and devotion to
work which, though always cheering, is sometimes hard. For
myself, I could not adequately express, but I hope they know
without words how much I have appreciated their loyal
support and their unity of spirit as they have worked
together with me during these last six months. The dark
cloud through which we have passed has caused us all as
colleagues to draw closer together, like children in a family
when the head has gone forth.”
 We find the same spirit in the account given in the
School Magazine of Mrs. Bryant’s election, on July 9,
as Miss Burstall concludes—

“It was a quiet day, and a very simple ceremony. There

was something of the sweetness and ease of home in it all,
and indeed we felt as if we were a family rather than a
school; and, as in the beautiful and sacred life of home we
do not speak of our loyalty and devotion, but act on them as
principles so certain as to need no expression, so it was
here. The day was a very happy one. Every one went about
her work with a new impulse of earnestness, a new
assurance of peaceful continuity. For the rest, the future will
speak, and the past is witness that the future will be good.”

On Prize Day, that last day of the old which was

the first day of the new era, Lady Frederick
Cavendish in her address dwelt especially on the
faith and sympathy of the Founder as the secret of
the success of her schools, finding here, as
everywhere, the true source of all great and lasting
work in the faith that uplifts and the love that unites.
Then from the bright past the speaker looked
beyond the darkly shadowed present to a future full
of hope in the work to come. None present on that
day will forget the inspiration of the closing words of
this address—words doubly strong as quoted by one
who had come through a great darkness into the
light: one who will always stand out as witness that a
heart emptied of joy may yet become a full channel
of blessing—

“What though the brightness dim, the glory fade,

The splendour vanish?—Not of these is made
The holy trust that to your charge is given,
Children of God, inheritors of heaven!
• • • • • •
A sacred burden is the life ye bear,
Look on it, lift it, bear it solemnly,
Stand up, and walk beneath it steadfastly,
Fall not for sorrow, falter not for sin,
But upward, onward, till the goal ye win.
God guide you, and God guard you all the way;
Children of light, set forth, set forth to-day!”
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