Tetrahedrally Bonded Amorphous

Carbon Films I Bernd Schultrich

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Springer Series in Materials Science 263

Bernd Schultrich

Tetrahedrally
Bonded
Amorphous
Carbon Films І
Basics, Structure and Preparation
Springer Series in Materials Science

Volume 263

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The Springer Series in Materials Science covers the complete spectrum of materials
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Bernd Schultrich

Tetrahedrally Bonded
Amorphous Carbon Films I
Basics, Structure and Preparation

123
Bernd Schultrich
Fraunhofer Institut
für Werkstoff- und Strahltechnik
Dresden
Germany

ISSN 0933-033X ISSN 2196-2812 (electronic)

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To Helga for your love, patience
and assistance
Preface

The technical world consists of contacting bodies, often in relative motion. That
means friction and wear. Without friction, the transmission of mechanical forces
would not work and wear is used for the machining of components. But in most
cases, friction and wear are undesired effects: Friction consumes power and wear
limits the long-term functionality. Hence, the reduction of friction and the protec-
tion against wear are essential topics in the technical development. Amorphous
carbon coatings represent promising solutions. They show very low friction without
any lubricants in combination with efficient wear protection.
The particular potential of carbon materials, especially demonstrated in the
fascinating properties of diamond, is based on the unique position of carbon under
all elements: its small atomic diameter (due to the low atomic number) and its
balanced electronic affinity (due to the existence of four valence electrons). This
combination leads to very strong covalent bonds, which in the case of the
three-dimensional diamond network realize the highest hardness of all materials.
But in accordance with thermodynamics, the usual carbon materials are graphitic
with low stiffness due to their configuration of two-dimensionally bonded layers.
The preparation of diamond structures is only possible under extreme high-pressure
high-temperature conditions (according to thermodynamics) or by clever use of the
kinetics of film growth. The kinetically controlled deposition of diamond films by
plasma-activated CVD from hydrocarbons is now state of the art. They are suc-
cessfully used in industry, for instance for cutting under heavy machining condi-
tions. But tribological applications of diamond films are limited by the rather low
deposition rate (increasing the costs) and especially the necessary high deposition
temperature (restricting the substrate materials).
For the broader utilization of the tribological potential of carbon coatings, a
number of challenging tasks must be solved:
– The realization of high hardness by a three-dimensional network of covalent
bonds as in diamond.
– The deposition with acceptable rate at sufficiently low temperatures, especially
on hardened steels.

vii
viii Preface

– The preparation of sufficient smooth surfaces.

– The realization of the superior frictional behavior also with lubricants.
– The avoidance of delamination even under severe tribological conditions.
Under industrial conditions, additional aspects must be considered:
– Acceptable deposition costs.
– Sufficient reproducibility by a stable and robust deposition process.
– Control of the environmental and health risks.
This book will demonstrate that tetrahedrally bonded amorphous carbon (ta-C),
the disordered counterpart of the crystalline diamond, is able to fulfill these
demands outstandingly. In ta-C, the carbon atoms are overwhelmingly bonded by
diamond-like bonds. Locally, the atomic arrangement shows (even though some
disturbed) the tetrahedral and to a minor part the trigonal environment, which on
larger scales represents the diamond and the graphite lattice. But these structural
units are not ordered over larger distances. The lacking constraints of a crystalline
order allow the combination of diamond-like and graphite-like bonds on the atomic
level. Thus, in amorphous carbon the complementary properties of diamond and
graphite (high and low hardness, high and low transparency, high and low electrical
resistivity, respectively) can be combined according to the specific demands.
The forerunners in the industrial use of amorphous carbon films were hydrogen
containing a-C:H films, prepared by plasma-enhanced CVD and now widely used,
especially for automotive components. The preparation of ta-C films with their
improved properties turned out to be essentially more challenging. The transfor-
mation of the academic recipe, the use of energetic carbon ions, into an industrial
technology demands the availability of ion sources with sufficient intensity.
Another critical point was the easy delamination of micrometer films due to the
extreme high compressive stresses. With advanced vacuum arc technologies, both
problems have been overcome and the broader introduction of ta-C films is now
running. Of special interest is not only the superior hardness (40–60 GPa in
comparison to 15–25 GPa of a-C:H), but also their specific surface interactions with
lubricants, leading to ultra-low friction even under boundary lubrication conditions.
This book tries to give a detailed and critical review of the current state of
tetrahedrally bonded amorphous carbon coatings with the orientation on their tri-
bological applications on the industrial level. The present first volume contains the
basics of ta-C films and the methods for their preparation. The introductory Part I
gives an overview of carbon, carbon materials, and carbon films, including diamond
and a-C:H. The corresponding structures and properties represent the reference for
the ta-C films, discussed in the following chapters. Part II treats the structural
development of ta-C films. The experimentally determined structure is compared
with the results of computer simulations and with the related structures of molten
carbon and amorphous silicon. The influence of the specific deposition conditions
(ion energy, substrate temperature, angle of incidence, deposition rate) is explained.
The combination of experimental investigations and theoretical modeling allows a
principal understanding of the growth of the ta-C structures and a semiempirical
Preface ix

quantitative description of the relevant dependencies. Part III discusses the vacuum
arc discharges, the most promising candidates for the industrial preparation of ta-C
coatings. Vacuum arcs are very efficient ion sources, but carbon turns out to be a
very problematic cathode material. Hence, particular arc methods, especially based
on pulsed discharges and/or magnetic filtering, must be developed. The potential
and the limitations of pulsed laser deposition and of sputtering for the ta-C depo-
sition are discussed in the final Part IV.
The projected second volume is mainly concerned with the mechanical prop-
erties (Part VI), the tribological behavior, and the use of ta-C films for tribological
applications (Part VII). The spectrum of the carbon films is markedly extended by
structural modifications, such as enhanced graphite-like fraction, incorporation of
hydrogen, nitrogen, or other nonmetals or alloying with metals. Preparation,
structure, and properties of these films are discussed in Part V. Finally in Part VIII,
an overview on functional properties of ta-C films and their application beyond
tribology will be given.
This book arose from my former work in managing the thin-film activities in the
Fraunhofer Institute for Material and Beam Technology (IWS), Dresden, always
with a strong industrial orientation. One of my main topics was the development of
industrially feasible technologies for the preparation of ta-C films, initially based on
pulsed laser irradiation, later on pulsed vacuum discharges. In the last years, these
developments, mainly based on the Laser-Arc technology, were well established in
industry. They demonstrate that the outstanding tribological potential of ta-C films
can be realized on the mass-production level.
According to my former academic career in theoretical physics, I was always
looking for rules, which could support the experimental optimization. The formation
of the ta-C films and their behavior in tribological systems are very complex phe-
nomena. Thus, it is a long way in the chain from the externally controllable tech-
nological parameters via the internal deposition conditions, the film structure, the
properties of the coated components to the aimed technological performance. Many
factors, often seeming bagatelles, as geometrical modifications or contaminations,
influence the final result. But nevertheless many subprocesses are at least qualita-
tively understood. That means, we are able to forecast the results (at least in their
tendency) for a broader variation of the input parameters. In the ideal case of com-
plete understanding of the underlying processes and of sufficient description of the
relevant conditions, the technological optimization would not demand any additional
experimental investigations. But usually neither our understanding nor our knowl-
edge of the detailed conditions are sufficient. Hence, a pragmatic way consists in
empirical rules, which are physically founded or suggested. They give a general
orientation on the tendencies to be expected and on the probable order of magnitude,
thus narrowing the necessary field of experimental variations. The comparison with
the theoretical expectations sharpens the critical view on the experimental results:
Deviations may hint on problems in the determination or evaluation of the experi-
mental data, on overlooked factors or (in the most interesting case) on new effects, up
to now not considered or on necessary modifications/improvements of the estab-
lished rules. Thus, it was my ambition, not only to give an extended description of the
x Preface

current state-of-the-art, but also to condense it into practicable (if possible quanti-
tative) rules and theses. Naturally, such aim is realizable only as a certain approxi-
mation; the conclusions are influenced by my personal experience and may be
modified by further work. But irrespective of such deficiencies, the evaluation of the
experimental results in light of estimated predictions makes daily research to an
exciting scientific adventure.
The present book, concentrating the existing ta-C facts and ideas, is mainly
thought for people of the carbon film community, to support their activities in the
further development of preparation, understanding, and application of the tetrahe-
drally bonded amorphous carbon films. In addition, the book demonstrates general
methods and problems of physical vapor deposition in depth on the specific
example of carbon coatings. Thus I hope, it will be generally of value for people,
using PVD methods.
I thank my co-workers in our carbon group, especially Dr. C.-F. Meyer,
Dr. H.-J. Scheibe, Dr. D. Schneider, Dr. P. Siemroth, Dr. Th. Stucky and Dr V. Weihnacht
for our longtime fruitful cooperation. The many collective projects, investigations, and
discussions laid the base for this book. I thank the editor, Dr. habil. Claus E. Ascheron, for
his continuous encouragement and insistence. Without his impetus, more than ten years
ago, I had not waged the adventure of this publication. Above all, I thank my dear wife, Dr.
Helga Schultrich, for her patience over all the years with stressing work and for her active
support.

Dresden, Germany Bernd Schultrich

July 2017
Contents

Part I Carbon Materials and Coatings

1 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1 Carbon Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3 Graphite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4 The Diamond-Graphite Transition . . . . . . . . . . . . . . . . . . . . . . 13
1.5 Engineering Carbon Materials . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.6 Melting of Carbon Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.7 Vaporization of Carbon Materials . . . . . . . . . . . . . . . . . . . . . . 29
1.8 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2 Diamond Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.1 Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.1.1 Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.1.2 Substrate Temperature . . . . . . . . . . . . . . . . . . . . . . . 43
2.1.3 Carbon/Hydrogen Ratio . . . . . . . . . . . . . . . . . . . . . . 43
2.2 Deposition Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.1 Hot Filament Deposition . . . . . . . . . . . . . . . . . . . . . . 47
2.2.2 Plasma Enhanced CVD . . . . . . . . . . . . . . . . . . . . . . . 48
2.2.3 Further Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.3 Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.3.1 Scratching Nucleation . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.2 Nucleation Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.3.3 Bias Enhanced Nucleation (BEN) . . . . . . . . . . . . . . . 52
2.4 Film Structure and Surface Morphology . . . . . . . . . . . . . . . . . . 54
2.4.1 Textured Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.4.2 Highly Oriented Diamond . . . . . . . . . . . . . . . . . . . . . 57

xi
xii Contents

2.4.3 Single Crystalline Films . . . . . . . . . . . . . . . . . . . . . . 58

2.4.4 Nanocrystalline Films . . . . . . . . . . . . . . . . . . . . . . . . 60
2.5 Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.5.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . 60
2.5.2 Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.5.3 Dynamic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.5.4 Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.5.5 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . 65
2.5.6 Optical Windows . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.5.7 Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.6 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3 Nanodiamond Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.1 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.1.1 Ultradense Nucleation . . . . . . . . . . . . . . . . . . . . . . . . 85
3.1.2 Renucleation by Reduced Hydrogen Etch . . . . . . . . . 87
3.1.3 Bias-Enhanced Growth . . . . . . . . . . . . . . . . . . . . . . . 88
3.1.4 Argon Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2 Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.2.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . 93
3.2.2 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . 93
3.2.3 Electrical Conductivity . . . . . . . . . . . . . . . . . . . . . . . 95
3.2.4 Transparency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.2.5 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.3 Low Temperature Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.3.1 Additional Reactive Elements . . . . . . . . . . . . . . . . . . 97
3.3.2 Increased Hydrocarbon Supply . . . . . . . . . . . . . . . . . 98
3.3.3 Intensified Precursor Excitation . . . . . . . . . . . . . . . . . 98
3.3.4 Argon Plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.4 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
4 Amorphous Carbon Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.1 Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.2 Hydrogen Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.3 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5 Hydrogenated Amorphous Carbon Films (a-C:H) . . . . . . . . . . . . . . 111
5.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
5.1.1 ta-C:H Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
5.1.2 Plasma Enhanced CVD (PECVD) . . . . . . . . . . . . . . . 112
5.1.3 Structural Classification . . . . . . . . . . . . . . . . . . . . . . 112
Contents xiii

5.2 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

5.2.1 Deposition Conditions . . . . . . . . . . . . . . . . . . . . . . . 113
5.2.2 Precursor Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
5.2.3 Frequency Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
5.2.4 rf PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.2.5 ECR PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.2.6 mf PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.2.7 dc PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.2.8 Arc Jet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.2.9 Atmospheric Plasma CVD . . . . . . . . . . . . . . . . . . . . 123
5.2.10 Electrochemical Deposition . . . . . . . . . . . . . . . . . . . . 124
5.3 Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
5.3.1 Surface Effects of Radicals and Ions . . . . . . . . . . . . . 127
5.3.2 Balance of Particle Fluxes . . . . . . . . . . . . . . . . . . . . . 127
5.3.3 Surface Roughness . . . . . . . . . . . . . . . . . . . . . . . . . . 128
5.4 Hydrogen Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
5.4.1 Unbound Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . 129
5.4.2 Hydrogen Incorporation . . . . . . . . . . . . . . . . . . . . . . 129
5.4.3 Hydrogen Reduction . . . . . . . . . . . . . . . . . . . . . . . . . 130
5.5 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.5.1 Bonding State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
5.5.2 Structure Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.5.3 Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
5.6 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
5.6.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . 139
5.6.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 144
5.6.3 Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
5.6.4 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . 151
5.6.5 Structural Stability . . . . . . . . . . . . . . . . . . . . . . . . . . 152
5.7 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
5.7.1 Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
5.7.2 Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
5.7.3 Transparent Protective Coatings . . . . . . . . . . . . . . . . . 156
5.7.4 Permeation Barriers . . . . . . . . . . . . . . . . . . . . . . . . . 157
5.7.5 Potential Applications . . . . . . . . . . . . . . . . . . . . . . . . 158
5.8 Nonmetal Containing a-C:H:X Films . . . . . . . . . . . . . . . . . . . . 158
5.8.1 a-C:H:N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5.8.2 a-C:H:Si, a-C:H:Si:O . . . . . . . . . . . . . . . . . . . . . . . . 160
5.8.3 a-C:H:F . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.8.4 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . 161
5.8.5 Friction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.8.6 Wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.8.7 Low j Dielectrics . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
xiv Contents

5.9 Metal Containing a-C:H:Me Films . . . . . . . . . . . . . . . . . . . . . . 166

5.9.1 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
5.9.2 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
5.9.3 Stress Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
5.9.4 Hardness and Stiffness . . . . . . . . . . . . . . . . . . . . . . . 173
5.9.5 Friction and Wear . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
5.9.6 Resistivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
5.10 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183

Part II Structural Development of ta-C Films

6 Structure of Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6.1 Structural Characterization of Amorphous Carbon . . . . . . . . . . . 195
6.1.1 sp3 Fraction s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
6.1.2 Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
6.1.3 Radial Density Function g(r) . . . . . . . . . . . . . . . . . . . 200
6.1.4 Additional Characteristics from Simulated
Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
6.1.5 Raman Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
6.1.6 Surface Acoustic Waves . . . . . . . . . . . . . . . . . . . . . . 212
6.2 Modelling of ta-C Structures . . . . . . . . . . . . . . . . . . . . . . . . . . 214
6.2.1 Simulation Procedure . . . . . . . . . . . . . . . . . . . . . . . . 214
6.2.2 Simulation Methods . . . . . . . . . . . . . . . . . . . . . . . . . 217
6.2.3 Interatomic Potentials . . . . . . . . . . . . . . . . . . . . . . . . 219
6.2.4 Reverse Monte Carlo Technique (RMC) . . . . . . . . . . 225
6.3 Structure of Amorphous Silicon . . . . . . . . . . . . . . . . . . . . . . . . 226
6.3.1 Hydrogen-Free a-Si . . . . . . . . . . . . . . . . . . . . . . . . . 226
6.3.2 Liquid Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
6.4 Structure of Liquid Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
6.5 Structure of ta-C with Highest sp3 Content . . . . . . . . . . . . . . . . 233
6.5.1 sp3 Content and Density . . . . . . . . . . . . . . . . . . . . . . 235
6.5.2 Radial Density Function . . . . . . . . . . . . . . . . . . . . . . 236
6.5.3 Additional Characteristics . . . . . . . . . . . . . . . . . . . . . 240
6.5.4 Comparison with a-Si . . . . . . . . . . . . . . . . . . . . . . . . 242
6.6 Structure of ta-C with Reduced sp3 Content . . . . . . . . . . . . . . . 243
6.6.1 Density of Amorphous Carbon . . . . . . . . . . . . . . . . . 244
6.6.2 Radial Density Function . . . . . . . . . . . . . . . . . . . . . . 247
6.6.3 Additional Characteristics . . . . . . . . . . . . . . . . . . . . . 251
6.6.4 Possible Nanodiamond Inclusions . . . . . . . . . . . . . . . 253
6.7 Top Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
6.8 Ultrathin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
Contents xv

6.9 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259

6.9.1 Structural Characterization of Amorphous Carbon . . . 259
6.9.2 Modelling of ta-C Structures . . . . . . . . . . . . . . . . . . . 261
6.9.3 Structure of Amorphous Silicon . . . . . . . . . . . . . . . . 261
6.9.4 Structure of Liquid Carbon . . . . . . . . . . . . . . . . . . . . 262
6.9.5 Structure of ta-C with Highest sp3 Content . . . . . . . . 262
6.9.6 Structure of ta-C with Reduced sp3 Content . . . . . . . . 263
6.9.7 Top Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
6.9.8 Ultrathin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
7 Influence of Deposition Conditions . . . . . . . . . . . . . . . . . . . . . . . . . 273
7.1 Ion Beam Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
7.2 Energy of the Incident Carbon Ions . . . . . . . . . . . . . . . . . . . . . 276
7.2.1 <20 eV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
7.2.2 20–600 eV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
7.2.3 600–10 keV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
7.2.4 >10 keV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
7.3 Angle of Incidence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
7.4 Substrate Temperature and Deposition Rate . . . . . . . . . . . . . . . 282
7.5 Layered Carbon Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.5.1 Designed Multilayer . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.5.2 Unintentional Layering . . . . . . . . . . . . . . . . . . . . . . . 292
7.6 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
8 Growth of ta-C Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
8.1 Subplantation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
8.1.1 Subplantation Growth Mode . . . . . . . . . . . . . . . . . . . 300
8.1.2 Parameter Range for Subplantation Growth . . . . . . . . 304
8.1.3 Penetration Threshold . . . . . . . . . . . . . . . . . . . . . . . . 308
8.1.4 Process Stages and Time Scales . . . . . . . . . . . . . . . . 309
8.2 Collision Cascade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
8.2.1 Binary Collision Approximation (BCA) . . . . . . . . . . . 314
8.2.2 Ion Track and Penetration Depth . . . . . . . . . . . . . . . . 317
8.2.3 Collision Cascade . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
8.2.4 Energy Dissipation . . . . . . . . . . . . . . . . . . . . . . . . . . 324
8.3 Impact-Induced Film Growth . . . . . . . . . . . . . . . . . . . . . . . . . . 327
8.3.1 Thermodynamical Estimations . . . . . . . . . . . . . . . . . . 327
8.3.2 Atomic Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . 329
8.3.3 Growth Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
8.3.4 Transient HP/HT Model . . . . . . . . . . . . . . . . . . . . . . 344
8.3.5 Phenomenological Description . . . . . . . . . . . . . . . . . . 346
xvi Contents

8.4 Thermally Modified Film Growth . . . . . . . . . . . . . . . . . . . . . . 348

8.4.1 Thermally Activated Relaxation . . . . . . . . . . . . . . . . . 349
8.5 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Explanations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
E1 Stopping Power S with Power Law (for (8.5),
(8.32)) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
E2 Binary Collision Approximation and TRIM
Program (for Sect. 8.2) . . . . . . . . . . . . . . . . . . . . . . . 358
E3 Film Growth by Subplantation (for (8.28)) . . . . . . . . . 360
E4 Kinchin-Pease Model (for Sect. 8.2) . . . . . . . . . . . . . 362
E5 Thermal Spike Model (for Sect. 8.3) . . . . . . . . . . . . . 363
E6 Surface Force on Point Defects (for Sect. 8.4) . . . . . . 365
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366

Part III Vacuum Arc Deposition of Carbon Films

9 Vacuum Arc Discharges with Carbon Cathodes . . . . . . . . . . . . . . . 373
9.1 Current-Voltage Characteristic . . . . . . . . . . . . . . . . . . . . . . . . . 375
9.2 Cathode Spots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
9.2.1 Spot Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
9.2.2 Energy Fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
9.2.3 Spot Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
9.2.4 Spot Dynamic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
9.3 Arc Plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
9.3.1 Plasma Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
9.3.2 Plasma State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
9.3.3 Ion Beam Acceleration . . . . . . . . . . . . . . . . . . . . . . . 399
9.3.4 Free Expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
9.3.5 Mass Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
9.3.6 Ion Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
9.4 Macroparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
9.4.1 Ejection of Macroparticles . . . . . . . . . . . . . . . . . . . . . 413
9.4.2 Flight of the Macroparticles . . . . . . . . . . . . . . . . . . . 418
9.4.3 Attachment of the Particles at the Substrate
Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
9.4.4 Incorporation of the Macroparticles
With Resulting Film Defects . . . . . . . . . . . . . . . . . . . 426
9.4.5 Elimination of Macroparticles from
the Growing Film . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
9.5 Peculiarities of Graphite Ablation by Vacuum
Arc Discharges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
9.6 Carbon Film Deposition with Vacuum Arc Discharges . . . . . . . 434
9.6.1 Unbiased Substrates . . . . . . . . . . . . . . . . . . . . . . . . . 434
9.6.2 Biased Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
Contents xvii

9.6.3 Substrate Temperature . . . . . . . . . . . . . . . . . . . . . . . 439

9.7 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
10 Methods of Vacuum Arc Deposition of ta-C Films . . . . . . . . . . . . . 453
10.1 Magnetically Driven DC Vacuum Arcs . . . . . . . . . . . . . . . . . . 453
10.2 Pulsed High Current Vacuum Arcs . . . . . . . . . . . . . . . . . . . . . 464
10.2.1 Expanding Spot System . . . . . . . . . . . . . . . . . . . . . . 464
10.2.2 Pecularities of Kiloampere Arc Currents . . . . . . . . . . 467
10.2.3 Influence of Fast Changing Arc Conditions . . . . . . . . 470
10.3 Arc Ignition with High Repetition Rates . . . . . . . . . . . . . . . . . 472
10.3.1 Contact Separation . . . . . . . . . . . . . . . . . . . . . . . . . . 473
10.3.2 Ignition by Insulator Breakdown . . . . . . . . . . . . . . . . 473
10.3.3 Ignition by Laser Pulses . . . . . . . . . . . . . . . . . . . . . . 477
10.3.4 Ignition by High Power Sputtering . . . . . . . . . . . . . . 481
10.3.5 Superpulsed DC Arc . . . . . . . . . . . . . . . . . . . . . . . . . 483
10.4 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
11 Vacuum Arc with Particle Filtering . . . . . . . . . . . . . . . . . . . . . . . . 493
11.1 Concept of Magnetic Filtering . . . . . . . . . . . . . . . . . . . . . . . . . 493
11.2 Macroparticle Filter Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . 498
11.3 Plasma Filter Transparency . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
11.4 Filter Systems for Minimum Macroparticle Transparency . . . . . 510
11.5 Filter Systems for Large Area Deposition . . . . . . . . . . . . . . . . . 514
11.6 Compact Arc Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
11.7 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
12 Special Arc Modes with Reduced Macroparticle Emission . . . . . . . 527
12.1 Distributed Arc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
12.2 Stationary Arc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533
12.3 Shunting Arc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
12.4 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
13 Vacuum Arc Equipment for Mass Production
of ta-C Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
13.1 Demands on Industrial Equipment for Coating of Tools and
Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
13.2 Technological Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
13.2.1 Pre-delivery Check . . . . . . . . . . . . . . . . . . . . . . . . . . 547
13.2.2 Wet Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
13.2.3 Loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
13.2.4 Evacuation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
xviii Contents

13.2.5 Plasma Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549

13.2.6 Interface Preparation . . . . . . . . . . . . . . . . . . . . . . . . . 552
13.2.7 Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552
13.2.8 Cooling and Venting . . . . . . . . . . . . . . . . . . . . . . . . 555
13.2.9 Final Inspection . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
13.2.10 Aftertreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
13.3 Industrial Vacuum Arc Devices for ta-C Deposition . . . . . . . . . 557
13.3.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
13.3.2 Medium Sized Cathodes . . . . . . . . . . . . . . . . . . . . . . 560
13.3.3 Large Cathodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
13.3.4 Deposition Rate for Rotating Carriers . . . . . . . . . . . . 572
13.4 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
Explanations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
E1 Deposition Rate on the Central Axis
(for 13.10, 13.13) . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
E2 Deposition Rate with Rotating Carriers
(for 13.16, 13.17) . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

Part IV Deposition of ta-C Films by Pulsed Laser and by Sputtering

14 Carbon Ablation with ns Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
14.1 PLD Arrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
14.2 Target Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
14.2.1 Energy Input . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
14.2.2 Surface Temperature . . . . . . . . . . . . . . . . . . . . . . . . . 594
14.3 Target Ablation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596
14.4 Plasma Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
14.5 Plasma Beam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
14.5.1 Plasma Propagation . . . . . . . . . . . . . . . . . . . . . . . . . 605
14.5.2 Angular Distribution . . . . . . . . . . . . . . . . . . . . . . . . . 608
14.5.3 Plasma Composition . . . . . . . . . . . . . . . . . . . . . . . . . 610
14.6 Plasma Energies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
14.6.1 KrF Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
14.6.2 ArF Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
14.6.3 Nd-YAG Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
14.6.4 VIS-Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
14.7 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
15 Carbon Film Deposition with ns Lasers . . . . . . . . . . . . . . . . . . . . . 633
15.1 Influence of Laser Intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
15.1.1 ArF Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
15.1.2 KrF Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
Contents xix

15.1.3 Nd-YAG Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639

15.2 Influence of Laser Wavelength . . . . . . . . . . . . . . . . . . . . . . . . 642
15.3 Macroparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
15.4 Influence of the Target Material . . . . . . . . . . . . . . . . . . . . . . . . 651
15.5 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 654
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 656
16 Related Deposition Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
16.1 Comparison of PLD and Vacuum Arc Deposition
of ta-C Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
16.1.1 Control of Target Erosion . . . . . . . . . . . . . . . . . . . . . 663
16.1.2 Carbon Plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
16.1.3 Deposition Efficiency . . . . . . . . . . . . . . . . . . . . . . . . 664
16.2 ns-PLD with Additional Activation . . . . . . . . . . . . . . . . . . . . . 666
16.3 Peculiarities of Carbon Deposition with ps and fs Lasers . . . . . 669
16.4 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
16.4.1 Comparison of ns-PLD and Vacuum Arc Deposition
of ta-C Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
16.4.2 ns-PLD with Additional Activation . . . . . . . . . . . . . . 674
16.4.3 ps and fs Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
17 Activated Sputter Deposition of ta-C Films . . . . . . . . . . . . . . . . . . . 679
17.1 Sputtering of Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679
17.1.1 Yield of Carbon Sputtering . . . . . . . . . . . . . . . . . . . . 680
17.1.2 Energy of the Sputtered Carbon Particles . . . . . . . . . . 684
17.2 Dual Ion Beam Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
17.3 Magnetron Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
17.3.1 Plasma Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
17.3.2 Balanced Magnetron . . . . . . . . . . . . . . . . . . . . . . . . . 690
17.3.3 Collisional Energy Loss . . . . . . . . . . . . . . . . . . . . . . 691
17.3.4 Particle Fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
17.3.5 Ion Beam Assisted Magnetron Sputtering . . . . . . . . . 695
17.3.6 Plasma Enhanced Magnetron Sputtering . . . . . . . . . . 696
17.3.7 Filtered Carbon Sputtering . . . . . . . . . . . . . . . . . . . . 705
17.3.8 ta-C Deposition in Industrial Magnetron Coaters . . . . 706
17.4 High Power Impulse Magnetron Sputtering . . . . . . . . . . . . . . . 710
17.5 Rules and Theses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
Appendix A: Specific Methods for ta-C Characterization . . . . . . . . . . . . 721
A.1 Ultrasonic Surface Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721
A.2 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 727
xx Contents

Appendix B: Values and Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741

B.1 Physical Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
B.2 Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
B.3 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
B.4 Carbon Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
B.5 Hydrogen-free Amorphous Carbon Films . . . . . . . . . . . . . . . . . . . . 743
B.6 Hydrogenated Amorphous Carbon Films . . . . . . . . . . . . . . . . . . . . 746
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
Acronyms

AEGD Arc-enhanced glow discharge

AES Auger electron spectroscopy
AFM Atomic force microscope
ART Activation relaxation technique
BCA Binary collision approximation
BEG Bias-enhanced growth
BEN Bias-enhanced nucleation
BSU Basic structural unit
BWF Breit–Wigner–Fano distribution
CFC Carbon-fiber-reinforced carbon
CMS Center of mass system
CPA Chirped-pulse amplifier
CPMD Car–Parrinello molecular dynamics
CVD Chemical vapor deposition
DBF Double-bend filter
DC Direct current
DFT Density functional theory
DFTB Density-functional-based tight binding
DIBS Dual-ion-beam sputtering
DLC Diamond-like carbon
EACVD Electron-assisted CVD
EB Electron beam
ECR Electron cyclotron resonance
EDIP Environment-dependent interaction potential
EDTP Environment-dependent tight binding
EELS Electron energy loss spectroscopy
FCVA Filtered cathodic vacuum arc
FRES Forward recoil elastic scattering
FWHM Full width at half maximum

xxi
xxii Acronyms

HDL High-density liquid

HFCVD Hot filament CVD
HIPIMS High-power impulse magnetron sputtering
HOD Highly oriented diamond
HOPG Highly oriented pyrolytic graphite
HPHT High-pressure high-temperature
HRTEM High-resolution transmission electron microscopy
IB Inverse bremsstrahlung
IBAD Ion-beam-assisted deposition
IBAM Ion-beam-assisted magnetron sputtering
IR Infrared spectral range
LAFAS Large area filtered arc sources
LARC Lateral rotating cathodes
LCBOP Long-range carbon bond-order potentials
LDA Local density approximation
LDL Low-density liquid
LMO Local molecular ordering
LTAVD Low-temperature arc vapor deposition
MC Monte Carlo method
MD Molecular dynamics
MEMS Microelectromechanical systems
mf medium frequency
MIR Medium infrared spectral range
MP Macroparticle
MPCVD Microwave plasma-enhanced CVD
MSIBD Mass-selected ion-beam deposition
NCD Nanocrystalline diamond
Nd-YAG Neodymium–yttrium aluminum garnet
NEXAFS Near-edge X-ray absorption fine structure
NMR Nuclear magnetic resonance
PC Polycarbonate
PCD Polycrystalline diamond
PECVD Plasma-enhanced CVD
PG Pyrolytic graphite
PIII Plasma immersion ion implantation
PLD Pulsed laser deposition
PMMA Polymethyl methacrylate
PVD Physical vapor deposition
RDF Radial density function
RED Radiation-enhanced diffusion
rf Radio frequency
RMC Reverse Monte Carlo
SAW Surface acoustic waves
SEM Scanning electron microscope
TB Tight binding
Acronyms xxiii

TOF Time-of-flight methods

TVG Triggered vacuum gaps
UBM Unbalanced magnetron sputtering
UNCD Ultrananocrystalline diamond
UV Ultraviolet spectral range
VIS Visible spectral range
XPS X-ray photoelectron spectroscopy
XRR X-ray reflectivity
YSZ Yttria-stabilized zirconia
Symbols

A Area
a Thermal diffusivity ð¼k=c  qÞ
Ap Plasma absorption
b Mobility
B Bulk modulus
B Magnetic field strength
bij Bond order
c Specific heat
c0 Light velocity
cX Atomic concentration of X
d Atomic distance
D Grain diameter
D(T) Diffusion constant
dc−s Cathode-substrate distance
dij Bond length
dL Diameter of the laser spot
DL Diameter of the laser bundle
DMP Size of macroparticles
E Energy of a particle system
E Young’s modulus
E0 =E/(1−m2)
Eg Band gap
EL Energy of the laser pulse
f Frequency
F(q) Reduced structure function
fA(rij) Attractive term of interaction potential
fei Electron–ion collision frequency
fL Focus length
fp Plasma frequency
fR(rij) Repulsive term of interaction potential

xxv
xxvi Symbols

fX Particle fraction of atoms X

G Molar free enthalpy
Gbou Boundary conductivity
G(r) Reduced radial density function
gð~rÞ Pair correlation function
g(r) Radial density function (RDF)
h Thickness
H Hardness
DH Molar evaporation enthalpy
hML Thickness of a monolayer
I Current
i Current density I/A
IX Intensity of the Raman peak (X = D, G, T)
I(q) Scattering intensity
j Particle flux density
J Particle flux
jL Laser intensity
jq Heat flux density
k Boltzmann constant
k(kÞ Extinction coefficient
L(e) Penetration depth (normal incident)
L0 ðe; 0Þ Penetration depth (inclined impact)
La Lateral dimensions of graphitic regions
lmfp Mean free path
lopt 1=a, optical penetration depth
M Atomic mass
m Particle mass
N Particle number
n Particle density (=N/V)
n(kÞ Refractive index
P Power
p Pressure
p(r) Probability
pv Saturation vapor pressure
q Activation energy
q Wavevector
q Particle charge
Q Charge
Q Coupling factor
qd Activation energy for rearrangement
R =8.314 J/(mol  K) molar gas constant
R Reflected fraction
Ra Mean roughness (absolute deviations)
rg Gyroradius
Symbols xxvii

Rn Mean distance of the n-nearest neighbors

Rq Root-mean-squared roughness
R(t) Radius of the spot system
RX Atomic radius of element X
Rz Averaged peak-to-peak roughness
s sp3 fraction (C–C bonds)
stot Total sp3 fraction (C–C bonds, C–H bonds)
si Length of the ion trajectory
S(q) Structure factor
S(e) Stopping power
S ðeÞ Stopping cross section
T Absolute temperature
T Collisional energy transfer
Tb Boiling temperature
tdiff Diffusion time
tdiss Dissipation time
Tg Glass temperature
timp Impact time
Tm Melting temperature
Tp Plasma temperature
Tr Ion transparency
u Drift velocity
U Voltage
-Ub Burning voltage
Ubias Bias voltage
Ures Voltage drop within the arc cathode
V Volume
v Atomic volume
v Velocity
V(r1, r2, …) Potential energy
vF Fermi velocity
vs Sound velocity
vspot Spot velocity
vX Volume fraction of phase X
w Linear growth rate (=dh/dt)
W Work function
wcoil Turn density of magnetic coils
wetch Linear etch rate (= −dx/dt)
Y Sputter yield
z Coordination number
Z Atomic number
zi Mean degree of ionization
a Metal–carbon ratio (=NMe/NC)
xxviii Symbols

a Loss factor of carbon plasma

a Linear thermal expansion coefficient
ag Mg/MC−1
aðkÞ ¼ 4pk/k, attenuation coefficient
b ¼ Ii =Iarc current ratio
d Collisional loss factor
e Particle energy
eb Binding energy = cohesive energy
ed Displacement energy
eion Ionization energy
ep Plasmon energy
esb Surface binding energy
e0 Vacuum permittivity
/ Potential
/iC =Ji/JC flux ratio
/p Plasma potential
c Duct attenuation factor
c Sticking coefficient
c Thermal volume expansion coefficient
C Full width at half maximum (FWHM)
ctr Energy transfer ratio in elastic collisions
ce Secondary electron yield
j Dielectric constant
j System coefficient
k Thermal conductivity
k Wavelength
kD Debye length
ke Electron mean free path
kCg Mean free path carbon in gas
l =Mi/MC
m Optical frequency
m Poisson’s ratio
m ¼ C0 =k Wave number
0 Angle of incidence
H Porosity
H Coverage degree
HD Debye temperature
q Mass density
q0 Specific electrical resistivity
rCg Cross section of carbon in gas
r0 Electrical conductivity
r Stress
Symbols xxix

r Standard deviation
s Pulse time
x Angular frequency
X Solid angle
n =jev/jem
Subscripts

a Anode
ads Adsorbed
ar Areal
b Burning
bou Boundary
c Cathode
col Collision
con Condensation
cr Critical
d Diamond
dep Deposition
diff Diffusion
e Electron
eff Effective
el Electronic
em Emission
en Energy
ev Evaporation
f Film
fin Finale
g Graphite
gr Grain
gro Ground
H Hydrogen
i Ion
imp Impact
IB Inverse bremsstrahlung
Kin Kinetic
L Laser
m Mass

xxxi
Another random document with
no related content on Scribd:
 The unfortunate major was traced to the house of Rainhill, where,
entering the garden, the pursuers soon found him. Gillespie, who
had got one of Anderson’s pistols, accompanied by Stevenson,
advanced upon the murderer, who came up with a fierce
countenance, asking what was the matter. 1694.
Paterson told him there had been a man
slain in Glasgow, and the murderer was supposed to be here: ‘If you
be he,’ added Paterson, ‘may God forgive you!’ Menzies replied: ‘It is
no business of yours;’ whereupon one of the others called out:
‘Dowhill, here is the man.’ Then the major, drawing his sword, and
using a horrible imprecation, came forward, crying: ‘What have the
rascals to do with me?’ The men retreated before him, and a pistol
was fired in self-defence, by which Menzies was slain. When
Paterson returned a minute after, he found him lying on his back,
dead, with his drawn sword across his breast.
Strange to say, Henry Fletcher, brother of Lord Salton, and
Lieutenant-colonel Hume, for the interest of his majesty’s forces,
raised a prosecution against the three Glasgow citizens for murder. It
ended in a verdict of Not proven.[133]

Previous to 1705, when the first professor Oct.

of anatomy was appointed in the university
of Edinburgh, there were only a few irregular attempts in the
Scottish capital to give instructions in that department of medical
education. We first hear of dissection of the dead body in our city in
the latter part of the year 1694, a little before which time the
celebrated Dr Archibald Pitcairn had left a distinguished position as
professor of medicine in the university of Leyden, and marrying an
Edinburgh lady, had been induced finally to settle there in practice.
On the 14th October, Pitcairn wrote to his friend, Dr Robert Gray of
London, that he was taking part in an effort to obtain subjects for
dissection from the town-council, requesting from them the bodies of
those who die in the correction-house called Paul’s Work, and have
none to bury them. ‘We offer,’ he says, ‘to wait on these poor for
nothing, and bury them after dissection at our own charges, which
now the town does; yet there is great opposition by the chief
surgeons, who neither eat hay nor suffer the oxen to eat it. I do
propose, if this be granted, to make better improvements in anatomy
than have been made at Leyden these thirty years; for I think most or
all anatomists have neglected or not known what was most useful for
a physician.’
The person ostensibly moving in this matter was Mr Alexander
Monteith, an eminent surgeon, and a friend of Pitcairn. In
compliance with his request, the town-council (October 24) gave him
a grant of the dead bodies of those dying in 1694.
the correction-house, and of foundlings who
die on the breast, allowing at the same time a room for dissection,
and freedom to inter the remains in the College Kirk cemetery, but
stipulating that he bury the intestines within forty-eight hours, and
the remainder of the body within ten days, and that his prelections
should only be during the winter half of the year.
Monteith’s brethren did not present any opposition to his
movement generally; they only disrelished his getting the Council’s
gift exclusively to himself. Proposing to give demonstrations in
anatomy also, they preferred a petition to the town-council, asking
the unclaimed bodies of persons dying in the streets, and foundlings
who died off the breast; and the request was complied with, on
condition of their undertaking to have a regular anatomical theatre
ready before the term of Michaelmas 1697.[134]
Such were the beginnings of the medical school of Edinburgh.

The Bass.
 REIGN OF WILLIAM III.: 1695–1702.

During this period, the affairs of Scotland were in a marked degree

subordinate to those of England. The king, absorbed in continental
wars and continental politics, paid little attention to his northern
kingdom; he left it chiefly to the care of its state-officers, using as a
medium of his own influence, William Carstares, a Presbyterian
minister of extraordinary worth, sincerity, and prudence, who had
gained his entire esteem and confidence, and who usually attended
him wherever he was. A parliament which sat in May 1695, was
chiefly occupied with the investigation of the Glencoe massacre, and
with measures connected with the rising commercial enterprise of
the country, including the formation of a native bank, and that of a
company for trading with Africa and the Indies. The latter of these
speculations was worked out in an expedition to Darien, and an
attempted settlement there, which, through English mercantile
jealousy, and the king’s indifference to Scottish interests, ended so
unfortunately as greatly to incense the Scottish nation, and increase
the party disaffected to the Revolution government. The misery
hence arising was increased by a dearth from a succession of bad
seasons. Nevertheless, this period will be found in our chronicle to
have been remarkable for the establishment of manufactories of
various kinds, and for various other industrial enterprises, shewing
that the national energies were beginning to take a decidedly new
direction. At the same time, instances of deplorable superstition,
cruelty, and intolerance were sufficiently numerous to attest that the
days of barbarism were not past.
Incessant efforts were made by the Jacobite party to procure the
restoration of King James, and the discontents excited by Darien
were greatly favourable to their views. Yet the heart of the middle
class throughout the more important provinces remained firm in
Presbyterianism, for which the Revolution government was the sole
guarantee; and in this lay an insuperable bar to all reactionary
projects. A war against France, which had begun immediately after
the Revolution (May 1689), was brought to a conclusion in
September 1697, by the treaty of Ryswick, which included an
acknowledgment by Louis XIV. of the title of King William to the
English throne. The exiled king, old and abandoned to ascetic
devotion, indulged a hope that he would outlive William, and be then
quietly recalled. He died, however, in September 1701, with only the
assurance of the French king in favour of the restoration of his son.
William survived him but a few months, dying of a fever and ague on
the 8th March 1702. His vigorous talents, his courage, his essential
mildness and tolerance, abated as they were by an unpopular
coldness of manners, are amply recognised in English history;
among the Scots, while Presbyterians thank him for the
establishment of their church, there is little feeling regarding the
Dutch king, besides a strong resentment of his concern in the affairs
of Glencoe and Darien.

This day, being Sunday, the Catholics of 1695. Feb. 17.

Edinburgh were so bold as to hold a
meeting for worship in the Canongate. It was fallen upon and
‘dissipat’ by the authorities, and the priest, Mr David Fairfoul, with
James De Canton and James Morris, fencing-masters, and John
Wilson of Spango, were committed to prison, while the Lord
Advocate obtained a list of other persons present. The Privy Council
ordered the four prisoners to be carried from the Canongate to the
Edinburgh Tolbooth, and appointed a committee to take what steps
it might think meet regarding the list of worshippers.
On the 28th February, the Council permitted the liberation of the
two fencing-masters, on assurance of their doing nothing offensive to
the government in future, under a penalty of five hundred merks. At
the same time, they ordained ‘Harry Graham, and his landlord,
James Blair, periwig-maker in Niddry’s Wynd; James Brown, son to
Hugh Brown, chirurgeon, and the said Hugh his father; John
Abercrombie, merchant in Edinburgh, and John Lamb in the Water
of Leith, to give bond in the same terms and under the same penalty;’
else to be kept in prison. Orders were given to search for John Laing,
writer, John Gordon, writer, and James Scott in the Canongate,
‘who, being also at the said meeting, have absconded.’ The priest
Fairfoul was treated with unexpected mercy, being liberated on
condition of banishment, not to return under a penalty of three
hundred pounds sterling.[135]

Robert Davidson, merchant in Ellon, Feb. 19.

Aberdeenshire, represented to the Privy
Council that he had been in a good way of merchandise, and
proprietor of a two-story house, when in the beginning of December
last some of Lord Carmichael’s dragoons were quartered upon him,
and deposited their powder in one of his low rooms. As they were
one morning dividing the powder, it caught 1695.
fire, and demolished the house, together
with his whole merchandise and household plenishing, carrying the
bed whereon he and his family lay to the top of the house, and
seriously injuring a relative who was living with him at the time, and
for the cost of whose cure he was answerable. Robert petitioned for
some compensation, and the Council—following its rule of a
vicarious beneficence—allowed him to raise a voluntary collection at
the church-doors of Aberdeenshire and the two adjacent counties.[136]

There never, perhaps, was any mystic Feb.

history better attested than that of ‘the
Rerrick Spirit.’ The tenant of the house, many of his neighbours, the
minister of the parish, several other clergymen, the proprietor of the
ground living half a mile off, all give their testimonies to the various
things which they ‘saw, heard, and felt.’ The air of actuality is helped
even by the local situation and its associations. It is in the same
parish with Dundrennan Abbey, where Queen Mary spent her last
night in Scotland. It is upon the same rock-bound coast which Scott
has described so graphically in his tale of Guy Mannering, which was
indeed founded on facts that occurred in this very parish. Collin, the
house of the laird, still exists, though passed into another family.
Very probably, the house of Andrew Mackie himself would also be
found by any one who had the curiosity to inquire for it; nor would
he fail, at the same time, to learn that the whole particulars of this
narration continue to be fresh in popular recollection, though four
generations have passed away since the event. Few narrations of the
kind have included occurrences and appearances which it was more
difficult to reconcile with the theory of trick or imposture.
Andrew Mackie, a mason, occupied a small farm, called Ring-croft,
on the estate of Collin, in the parish of Rerrick, and stewartry of
Kirkcudbright. He is spoken of as a man ‘honest, civil, and harmless
beyond many of his neighbours,’ and we learn incidentally that he
had a wife and some children. In the course of the month of February
1695, Andrew was surprised to find his young cattle frequently loose
in the byre, and their bindings broken. Attributing it to their
unruliness, he got stronger bindings; but still they were found loose
in the morning. Then he removed the beasts to another place; and
when he went to see them next morning, he 1695.
found one bound up with a hair tether to
the roof-beam, so strait, that its feet were lifted off the ground. Just
about this time, too, the family were awakened one night with a smell
of smoke; and when they got up, they found a quantity of peats lying
on the floor, and partially kindled. It seemed evident that some
mischievous agent was at work in Ring-croft; but as yet nothing
superhuman was in the surmises of the family.
On Wednesday, the 7th of March, a number of stones were thrown
in the house—‘in all places of it’—and no one could tell whence they
came, or who threw them. This continued during day and night, but
mostly during the night, for several days, the stones often hitting the
members of the family, but always softly, as if they had less than half
their natural weight. A kind of fear began to take possession of the
little household, and the father’s fireside devotions waxed in
earnestness. Here, however, a new fact was developed: the stone-
throwing was worst when the family was at prayers. On the Saturday
evening, the family being for some time without, one or two of the
children, on entering, were startled to observe what appeared a
stranger sitting at the fireside, with a blanket about him. They were
afraid, and hesitated; but the youngest, who was only nine or ten
years of age, chid the rest for their timidity, saying: ‘Let us sain
[bless] ourselves, and then there is no ground to fear it!’ He
perceived that the blanket around the figure was his. Having blessed
himself, he ran forward, and pulled away the blanket, saying: ‘Be
what it will, it hath nothing to do with my blanket.’ It was found to be
a four-footed stool set on end, and the blanket cast over it.
Attending church on Sunday, Andrew Mackie took an opportunity,
after service, of informing the minister, Mr Telfair, how his house
had been disturbed for the last four days. The reverend gentleman
consequently visited Ring-croft on Tuesday. He prayed twice,
without experiencing any trouble; but soon after, as he stood
conversing with some people at the end of the barn, he saw two
stones fall on the croft near by, and presently one came from the
house to tell that the pelting within doors had become worse than
ever. He went in, prayed again, and was hit several times by the
stones, but without being hurt. After this there was quiet for several
days. On Sunday it began again, and worse than before, for now the
stones were larger, and where they hit, they gave pain. On the
ensuing Wednesday, the minister revisited 1695.
the house, and stayed a great part of the
night, during which he was ‘greatly troubled.’ ‘Stones and several
other things,’ says he, ‘were thrown at me; I was struck several times
on the sides and shoulders very sharply with a great staff, so that
those who were present heard the noise of the strokes. That night it
threw off the bed-side, and rapped upon the chests and boards as one
calling for access. As I was at prayer, leaning on a bed-side, I felt
something pressing up my arm. I, casting my eyes thither, perceived
a little white hand and arm, from the elbow down, but presently it
evanished.’
The neighbours now began to come about the house, to gratify
their curiosity or express sympathy; and both when they were within
doors, and when they were approaching or departing, they were
severely pelted. Mackie himself got a blow from a stone, which
wounded his forehead. After several apparent efforts of a visionary
being to seize him by the shoulder, he was griped fast by the hair of
the head, and ‘he thought something like nails scratched his skin.’
This, however, was little in comparison to what happened with some
of the neighbours, for, as attested by ‘Andrew Tait in Torr,’ they were
seized and dragged up and down the house by the clothes. ‘It griped
one John Keig, miller in Auchencairn, so by the side, that he
entreated his neighbours to help: it cried it would rive [tear] the side
from him. That night it lifted the clothes off the children, as they
were sleeping in bed, and beat them on the hips as if it had been with
one’s hand, so that all who were in the house heard it. The door-bar
and other things would go thorough the house, as if a person had
been carrying them in his hand; yet nothing seen doing it. It also
rattled on chests and bed-sides with a staff, and made a great noise.’
‘At night it cried, “Whisht! whisht!” at every sentence in the close of
prayer; and it whistled so distinctly, that the dog barked and ran to
the door, as if one had been calling to hound him.’
At the request of the laird, Charles M‘Lellan of Collin, a number of
ministers put up public prayers on account of these strange
occurrences, and on the 4th of April two came to the house to see
what they could do in behalf of the family. They spent the night in
fasting and prayer, but with no other apparent effect than that of
rendering the supposed spirit more ‘cruel.’ One of the reverend
gentlemen got a wound in the head from a stone, and the other had
his wig pulled off, and received several sore blows, which, however,
were healed quickly. A fiery peat was 1695.
thrown amongst the people, and in the
morning when they arose from prayer, ‘the stones poured down on
all who were in the house to their hurt.’
Two days after, the affair took a new turn, when Mackie’s wife was
induced to lift a stone which she found loose at the threshold of the
house, and perceived underneath ‘seven small bones, with blood, and
some flesh, all closed in a piece of old soiled paper;’ the blood being
fresh and bright. She presently ran to the laird’s house, about a
quarter of a mile distant, to fetch him; and while she was gone, the
spirit became worse than ever, ‘throwing stones and fire-balls in and
about the house; but the fire, as it lighted, did evanish. It thrust a
staff through the wall above the children in bed, shook it over them,
and groaned.’ The laird came and lifted the bones and flesh, after
which the trouble ceased for a little time. Next day, however, being
Sunday, it recommenced with throwing of stones and other heavy
articles, and set the house twice on fire. In the evening, when the
eldest boy was coming home, ‘an extraordinary light fell about him,
and went before him to the house, with a swift motion.’
On the ensuing morning, the 8th April, Mackie found in his close a
letter written and sealed with blood, superscribed thus: ‘3 years tho
shall have to repent a net it well.’ Within he read: ‘Wo be to the
Cotlland Repent and tak warning for the door of haven ar all Redy
bart against the I am sent for a warning to the to fllee to god yet
troublt shallt this man be for twenty days a 3 rpent rpent Scotland
or els tow shall.’[137]
Following up the old notion regarding the touching of a murdered
person in order to discover the murderer, all the surviving persons
who had lived in the house during the twenty-eight years of its
existence, were convened by appointment of the civil magistrate
before Charles M‘Lellan of Collin, ‘and did all touch the bones,’ but
without any result.
On a committee of five ministers coming two days after to the
house, the disturbing agency increased much in violence. According
to the parish minister, Telfair, who was present on this occasion, ‘It
came often with such force, that it made all the house shake; it brake
a hole through the timber and thatch of the 1695.
roof, and poured in great stones, one
whereof, more than a quarter weight, fell upon Mr James Monteath
his back, yet he was not hurt.’ When a guard was set upon the hole in
the roof, outside, it broke another hole through the gable from the
barn, and threw stones in through that channel. ‘It griped and
handled the legs of some, as with a man’s hand; it hoised up the feet
of others, while standing on the ground; thus it did to William
Lennox of Millhouse, myself, and others.’
After this, the disturbances went on with little variation of effect
for a week or more. A pedler felt a hand thrust into his pocket.
Furniture was dragged about. Seeing a meal-sieve flying about the
house, Mackie took hold of it, when the skin was immediately torn
out. Several people were wounded with the stones. Groaning,
whistling, and cries of Whisht—Bo, bo—and Kuck, kuck! were
frequently heard. Men, while praying, were over and over again lifted
up from the ground. While Mackie was thrashing in the barn, some
straw was set fire to, and staves were thrust at him through the wall.
When any person was hit by a stone, a voice was heard saying: ‘Take
that till you get more;’ and another was sure to come immediately.
On the 24th of April, there was a fast and humiliation in the parish
on account of the demonstrations at Ring-croft; and on that day the
violences were more than ever extreme, insomuch that the family
feared they should be killed by the stones. ‘On the 26th, it threw
stones in the evening, and knocked on a chest several times, as one to
have access, and began to speak, and call those who were sitting in
the house witches and rooks, and said it would take them to hell. The
people then in the house said among themselves: “If it had any to
speak to it, now it would speak.” In the meantime, Andrew Mackie
was sleeping. They wakened him, and then he, hearing it say: “Thou
shalt be troubled till Tuesday,” asked, “Who gave thee a
commission?” It answered: “God gave me a commission, and I am
sent to warn the land to repent, for a judgment is to come, if the land
do not quickly repent;” and commanded him to reveal it upon his
peril. And if the land did not repent, it said it would go to its father,
and get a commission to return with a hundred worse than itself, and
it would trouble every particular family in the land. Andrew Mackie
said: “If I should tell this, I would not be believed.” Then it said:
“Fetch [your] betters; fetch the minister of 1695.
the parish, and two honest men on
Tuesday’s night, and I shall declare before them what I have to say.”
Then it said: “Praise me, and I will whistle to you; worship me, and I
will trouble you no more.” Then Andrew Mackie said: “The Lord,
who delivered the three children out of the fiery furnace, deliver me
and mine this night from the temptations of Satan!” It replied: “You
might as well have said, Shadrach, Meshach, and Abednego.”’ On a
humble person present here putting in a word, the voice told him he
was ill-bred to interfere in other people’s discourse. ‘It likewise said:
“Remove your goods, for I will burn the house.”’
The house was actually set on fire seven times next day, and the
care of the inmates preventing damage of this kind from extending,
the end of the house was pulled down in the evening, so that the
family was forced to spend the night in the barn. On the second next
day, the house being again set fire to several times, Mackie carefully
extinguished all fires about the place, and poured water upon his
hearth; yet after this, when there was no fire within a quarter of a
mile, the conflagrations, as was alleged, were renewed several times.
The period announced in the bloody letter of the 8th instant was
now approaching, and in a conversation with Mackie, the supposed
spirit good-naturedly informed him that, ‘except some casting of
stones on Tuesday to fulfil the promise,’ he should have no more
trouble. Tuesday, being the 30th of April, was the twenty-third day
from the finding of the letter. That night, Charles M‘Lellan of Collin
and several neighbours were in the barn. As he was at prayer, he
‘observed a black thing in the corner of the barn, and it did increase,
as if it would fill the whole house. He could not discern it to have any
form, but as if it had been a black cloud; it was affrighting to them
all. Then it threw bear-chaff and mud in their faces, and afterwards
did grip severals who were in the house by the middle of the body, by
the arms, and other parts of their bodies, so strait, that some said for
five days thereafter they thought they felt those grips.’ Such,
excepting the firing of a sheep-cot next day, was the last that was
seen, heard, or felt of the Rerrick Spirit.
So great was the impression made by these incidents, that early in
the ensuing year Mr Telfair published an account of them in a small
pamphlet, which went through a second edition in Scotland, and was
reprinted, with alterations of language, in 1695.
[138]
London. At the end appeared the
attestations of those who ‘saw, heard, and felt’ the various things
stated—namely, ‘Mr Andrew Ewart, minister at Kells; Mr James
Monteath, minister at Borgue; Mr John Murdo, minister at
Crossmichael; Mr Samuel Stirling, minister at Parton; Mr William
Falconer, minister at Kelton; Charles M‘Lellan of Collin, William
Lennox of Millhouse, Andrew and John Tait in Torr, John Cairns in
Hardhills, William Macminn, John Corsby, Thomas Macminn,
Andrew Paline, &c.’ It may be remarked, that for each particular
statement in the Relation, the names of the special witnesses are
given; and their collected names are appended, as to a solemn
document in which soul and conscience were concerned.

The degree of respect felt by the Mar. 19.

authorities of this age for the rights of the
individual, is shewn very strikingly in a custom which was now and
for a considerable time after largely practised, of compromising with
degraded and imputedly criminal persons for banishment to the
American plantations. For example, at this date, thirty-two women of
evil fame, residing in Edinburgh, were brought before the
magistrates as a moral nuisance. We do not know what could have
been done to them beyond whipping and hard labour; yet they were
fain to agree that, instead of any other punishment, they should be
banished to America, and arrangements for that purpose were
immediately made.
In the ensuing June, a poor woman of the same sort, named Janet
Cook, residing in Leith, was denounced for offences in which a father
and son were associated—a turpitude which excited a religious
horror, and caused her to be regarded as a criminal of the highest
class. The Lord Advocate reported of Janet to the Privy Council, that
she had been put under the consideration of the Lords of Justiciary,
as a person against whom ‘probation could not be found,’ but that
the Lords were nevertheless ‘of opinion she might be banished the
kingdom,’ and she herself had ‘consented to her banishment.’ The
Lords of the Privy Council seem to have had no more difficulty about
the case than those of the Court of 1695.
Justiciary had had; they ordered that Janet
should depart furth of the kingdom and not return, ‘under the
highest pains and penalties.’
In January 1696, a woman named Elizabeth Waterstone,
imprisoned on a charge identical in all respects with the above, was,
in like manner, without trial, banished, with her own consent, to the
plantations.
On the 7th of February 1697, four boys who were notorious
thieves, and eight women who were that and worse, were called
before the magistrates of Edinburgh, and ‘interrogat whether or not
they would consent freely to their own banishment furth of this
kingdom, and go to his majesty’s plantations in America.’ ‘They one
and all freely and unanimously consented so to do,’ and
arrangements were made by the Privy Council for their deportation
accordingly. It was only ordained regarding the boys that Lord Teviot
might engage them as recruits for Flanders, in which case he was
immediately to commence maintaining them.
On the 15th February 1698, Robert Alexander, ‘a notorious horse-
stealer,’ now in prison, was willing to appease justice by consenting
to banishment without trial. He likewise made discoveries enabling
several countrymen to recover their horses. The Privy Council
therefore ordained him to be transported by the first ship to the
plantations of America, not to return thence under pain of death.
William Baillie, ‘ane Egyptian,’ prisoner in the Tolbooth of
Edinburgh, but regarding whom we hear of no specific offence and
no trial, was summarily ordered (Sep. 12, 1699) to be transported in
the first ship going to the plantations, the skipper to be allowed a
proper gratuity from the treasury, and at the same time to give
caution for five hundred merks that he would produce a certificate of
the man being landed in America.[139]
It was long before justice in Scotland took any qualm about this
free-and-easy way of dealing with accused persons. So late as 1732,
two men of humble rank—Henderson, a sedan-carrier, and
Hamilton, a street-cadie—suspected of being accessory to the
murder of an exciseman, having petitioned for banishment before
trial, were sent from the jail in Edinburgh to Glasgow, there to wait a
vessel for the plantations.[140]
The Earl of Home, as a dangerous person, 1695. Apr. 3.
had for some time been confined to his
house of the Hirsel, near Coldstream; but now he was required to
enter himself prisoner in Edinburgh Castle. He represented himself
as under such indisposition of body as to make this unendurable, and
the Council therefore ordered Dr Sir Thomas Burnet, the king’s
physician, to take a chirurgeon with him to the Hirsel, and inquire
into the state of his lordship’s health. The doctor and surgeon
reported in such terms that the earl was allowed to remain at the
Hirsel, but not without caution to the extent of two thousand pounds
sterling. For their pains in travelling fifty miles and back, and giving
this report, the Council allowed Dr Burnet two hundred merks (£11,
2s. 2d.), and Gideon Elliot, chirurgeon, one hundred merks.[141]

A hership of cattle having taken place on May 20.

the lands of Lord Rollo, in Perthshire, the
Master of Rollo was pleased to prosecute the matter a little more
energetically than was convenient to some of his neighbours. He
seems to have particularly excited the resentment of James
Edmonstoun of Newton, one of whose tenants was found in
possession of a cow reclaimed as part of the hership. Newton, being
soon after at the house of Clavidge, spoke some despiteful words
regarding the Master, which were afterwards taken notice of. At the
same house, about the same time, Patrick Graham, younger of
Inchbrakie, spoke in the like angry terms of the Master. ‘It has been
noised in the country,’ said he, ‘that I have courted the Master of
Rollo, and fawned upon him; but when occasion serves, something
different will be seen.’
These two hot-headed men spent a couple of days together at
Ryecroft, a house of young Inchbrakie, and probably there inflamed
their common resentment by talking over their grievances. On the
day noted in the margin, hearing that the Master of Rollo was to go
in the afternoon to Invermay House, they rode to his house of
Duncrub, and from that place accompanied him to Invermay,
together with the Laird of Clavidge and a gentleman named
M‘Naughton. Inchbrakie was remarked to have no sword, while his
companion Newton was provided with one. Supping at the
hospitable board of Invermay, these two conducted themselves much
in the manner of men seeking a quarrel. Inchbrakie said to the
Master: ‘Master, although John Stewart killed and salted two of your
kine, you surely will not pursue him, since 1695.
your father and his Miss ate them!’
Hereupon Clavidge remarked that this was not table-talk; to which
Newton made answer: ‘I think you are owning that.’ Then Inchbrakie
and Newton were observed to whisper together, and the latter was
heard saying: ‘I will not baulk you, Inchie.’ Afterwards, they went out
together, and by and by returned to table. What was the subject of
their conversation during absence, might only too easily be inferred
from what followed.
At ten o’clock the party broke up, and the strangers mounted their
horses, to ride to their respective homes. The Laird of Invermay,
having observed some mischief brewing in the mind of Newton,
endeavoured to make him stay for the night, but without success.
The Master, Clavidge, and M‘Naughton rode on, with Inchbrakie a
little in front of them. When Newton came up, Inchbrakie and he
turned a little aside, and Newton was then observed to loose his belt
and give his sword to Inchbrakie. Then riding on to the rest of the
party, he contrived to lead Clavidge and M‘Naughton a little ahead,
and commenced speaking noisily about some trivial matter. Hearing,
however, the clashing of two swords behind them, Clavidge and
M‘Naughton turned back, along with Newton, and there saw the
Master of Rollo fallen on his knees, while Inchbrakie stood over him.
The latter called out to Newton, ‘He has got it.’ Clavidge rushed to
sustain the sinking man, while Inchbrakie and Newton went apart
and interchanged a few hurried sentences. Presently Newton came
up again, when Clavidge, perceiving that the Master was wounded to
the death, cried out: ‘O God, such a horrid murder was never seen!’
To this Newton, standing coolly by, said: ‘I think not so—I think it
has been fair.’ The poor Master seems to have died immediately, and
then Newton went again aside with Inchbrakie, gave him his own
hat, and assisted him to escape. In the morning, when the two
swords were found upon the ground, the bloody one proved to be
Newton’s.
Inchbrakie fled that night to the house of one John Buchanan,
whom he told that he had killed the Master of Rollo, adding, with
tokens of remorse: ‘Wo worth Newton—wo worth the company!’ and
stating further that Newton had egged him on, and given him a
weapon, when he would rather have declined fighting.
Inchbrakie escaped abroad, and was outlawed, but, procuring a
remission, returned to his country in 1720. 1695.
[142]
James Edmonstoun of Newton was
tried (Aug. 6, 1695) for accession to the murder of John Master of
Rollo, and condemned to banishment for life.[143] It is stated that,
nevertheless, he carried the royal standard of James VIII. at the
battle of Sheriffmuir, and even after that event, lived many years on
his own estate in Strathearn.[144]

The Estates at this date advert to the fact May.

that sundry lands lying along the sea-coast
had been ruined, in consequence of their being overwhelmed with
sand driven from adjacent sand-hills, ‘the which has been mainly
occasioned by the pulling up by the roots of bent, juniper, and broom
bushes, which did loose and break the surface and scroof of the sand-
hills.’ In particular, ‘the barony of Cowbin and house and yards
thereof, lying in the sheriffdom of Elgin, is quite ruined and
overspread with sand,’ brought upon it by the aforesaid cause.
Penalties were accordingly decreed for such as should hereafter pull
up bent or juniper bushes on the coast sand-hills.[145]
A remarkable geological phenomenon, resulting in the ruin of a
family of Morayland gentry, is here in question. We learn from an act
of parliament, passed two months later, that, within the preceding
twenty years, two-thirds of the estate of Culbin had been
overwhelmed with blown sand, so that no trace of the manor-house,
yards, orchards, or mains thereof, was now to be seen, though
formerly ‘as considerable as many in the country of Moray.’
Alexander Kinnaird of Culbin now represented to the parliament,
that full cess was still charged for his lands, being nearly as much as
the remainder of them produced to him in rent; and he petitioned
that his unfortunate estate might, in consideration of his
extraordinary misfortune, be altogether exempted from cess. Three
years after this date, we hear of the remaining fourth part of Culbin
as sold for the benefit of the creditors of the proprietor, and himself
suing to parliament for a personal protection. In time, the entire ruin
of the good old barony was completed. Hugh Miller says: ‘I have
wandered for hours amid the sandwastes of this ruined barony, and
seen only a few stunted bushes of broom, and a few scattered tufts of
withered bent, occupying, amid utter 1695.
barrenness, the place of what, in the middle
of the seventeenth century, had been the richest fields of the rich
province of Moray; and, where the winds had hollowed out the sand,
I have detected, uncovered for a few yards-breadth, portions of the
buried furrows, sorely dried into the consistence of sun-burned
brick, but largely charged with the seeds of the common cornfield
weeds of the country, that, as ascertained by experiment by the late
Sir Thomas Dick Lauder, still retain their vitality. It is said that an
antique dove-cot, in front of the huge sand-wreath which enveloped
the manor-house, continued to present the top of its peaked roof
over the sand, as a foundered vessel sometimes exhibits its vane over
the waves, until the year 1760. The traditions of the district testify
that, for many years after the orchard had been enveloped, the
topmost branches of the fruit-trees, barely seen over the surface,
continued each spring languidly to throw out bud and blossom; and
it is a curious circumstance, that in the neighbouring churchyard of
Dike there is a sepulchral monument of the Culbin family, which,
though it does not date beyond the reign of James VI., was erected by
a lord and lady of the lost barony, at a time when they seem to have
had no suspicion of the utter ruin which was coming on their house.
The quaint inscription runs as follows:
VALTER : KINNAIRD : ELIZABETH : INNES : 1613 :
 THE : BVILDARS : OF : THIS : BED : OF : STANE :
AR : LAIRD : AND : LADIE : OF : COVBINE :
QVHILK : TVA : AND : THARS : QVHANE : BRAITHE IS : GANE :
PLEIS : GOD : VIL : SLEIP : THIS : BED : VITHIN :

I refer to these facts, though they belong certainly to no very remote

age in the past history of our country, chiefly to shew that in what
may be termed the geological formations of the human period, very
curious fossils may be already deposited, awaiting the researches of
the future. As we now find, in raising blocks of stone from the
quarry, water-rippled surfaces lying beneath, fretted by the tracks of
ancient birds and reptiles, there is a time coming when, under thick
beds of stone, there may be detected fields and orchards, cottages,
manor-houses, and churches—the memorials of nations that have
perished, and of a condition of things and a stage of society that have
for ever passed away.’[146]

The same advantages of situation which June 4.

are now thought to 1695.
adapt Peterhead
for a harbour of refuge for storm-beset vessels—placed centrally and
prominently on the east coast of Scotland—rendered it very
serviceable in affording shelter to vessels pursued by those French
privateers which, during the present war, were continually scouring
the German Ocean. Very lately, four English vessels returning from
Virginia and other foreign plantations with rich commodities, would
have inevitably been taken if they had not got into Peterhead
harbour, and been protected there by the fortifications and the
‘resoluteness’ of the inhabitants. The spirit manifested in keeping up
the defences, and maintaining a constant guard and watch at the
harbour, had incensed the privateers not a little; and one Dunkirker
of thirty-four guns took occasion last summer to fire twenty-two
great balls at the town, nor did he depart without vowing (as
afterwards reported by a Scottish prisoner on board) to return and
do his endeavour to set it in a flame. The people, feeling their danger,
and exhausted with expensive furnishings and watchings, now
petitioned the Privy Council for a little military protection—which
was readily granted.[147]
 As political troubles subsided in Scotland, June.
the spirit of mercantile enterprise rose and
gained strength. The native feelings of this kind were of course
stimulated by the spectacle of success presented in England by the
East India Company, and the active trade carried on with the
colonies. These sources of profit were monopolies; but Scotland
inquired, since she was an independent state, what was to hinder her
to have similar sources of profit established by her own legislature.
The dawnings of this spirit are seen in an act passed in the Scottish
parliament in 1693, wherein it is declared, ‘That merchants may
enter into societies and companies for carrying on trade as to any
sort of goods to whatsoever countries not being at war with their
majesties, where trade is in use to be, and particularly, besides the
kingdoms of Europe, to the East and West Indies, to the Straits and
Mediterranean, or upon the coast of Africa, or elsewhere,’ and
promising to such companies letters-patent for privileges and other
encouragements, as well as protection in case of their being attacked
or injured. Amongst a few persons favouring this spirit, was one of
notable character and history—William Paterson—a native of
Scotland, but now practising merchandise 1695.
in London—a most active genius, well
acquainted with distant countries, not visionary, animated, on the
contrary, by sound commercial principles, yet living, unfortunately
for himself, before the time when there was either intelligence or
means for the successful carrying out of great mercantile adventures.
Paterson, in the early part of this year, had gained for himself a
historical fame by projecting and helping to establish the Bank of
England. For his native country he at the same time projected what
he hoped would prove a second East India Company.
At the date noted, an act passed the Scottish parliament, forming
certain persons named into an incorporation, under the name of The
Company of Scotland Trading to Africa and the Indies, who should
be enabled to ‘plant colonies, and build cities and forts, in any
countries in Asia, Africa, or America, not possest by any European
sovereign,’ ‘by consent of the natives and inhabitants thereof,’ and to
take all proper measures for their own protection and the
advancement of their special objects, only acknowledging the
supremacy of the king by the annual payment of a hogshead of
tobacco. It was scrupulously arranged, however, that at least one half
of the stock of this Company should be subscribed for by Scotsmen
residing either at home or abroad.
Although the war pressed sorely on the resources of England,
Paterson calculated securely that there was enough of spare capital
and enterprise in London to cause the new Scottish trading scheme
to be taken up readily there. When the books for subscription were
opened in October, the whole £300,000 offered to the English
merchants was at once appropriated. By this time, the fears of the
East India Company and of the English mercantile class generally
had been roused; it was believed that the Scottish adventurers would
compete with them destructively in every place where they now
enjoyed a lucrative trade. The parliament took up the cry, and voted
that the noblemen and gentlemen named in the Scottish act were
guilty of a high crime and misdemeanour. Irritated rather than
terrified by this denunciation, these gentlemen calmly proceeded
with their business in Scotland. The subscription books being opened
on the 26th of February 1696, the taking up of the stock became
something like a national movement. It scarcely appeared that the
country was a poor one. Noblemen, country gentlemen, merchants,
professional men, corporations of every kind, flocked to put down
their names for various sums according to their ability, till not
merely the £300,000 devoted to Scotsmen 1695.
was engaged for, but some additional
capital besides.[148] In a list before me, with the sums added up, I find
the total is £336,390 sterling; but, of course, the advance of this large
sum was contemplated as to be spread over a considerable space of
time, the first instalment of 25 per cent. being alone payable within
1696.
Meanwhile the furious denunciations of the English parliament
proved a thorough discouragement to the project in London, and
nearly the whole of the stockholders there silently withdrew from it;
under the same influence, the merchants of Hamburg were induced
to withdraw their support and co-operation, leaving Scotland to work
out her own plans by herself.
 African Company’s House at Bristo Port, Edinburgh.

She proceeded to do so with a courage much to be admired. A

handsome house for the conducting of the Company’s business was
erected; schemes for trade with Greenland, with Archangel, with the
Gold Coast, were considered; the qualities of goods, possible
improvements of machinery, the extent of 1695.
the production of foreign wares, were all the
subject of careful inquiry. Under the glow of a new national object,
old grudges and antipathies were forgotten. William Paterson,
indeed, had set the pattern of a non-sectarian feeling from the
beginning, for, writing from London to the Lord Provost of
Edinburgh in July 1695, we find him using this strain of language,
hitherto unwonted in Scotland: ‘Above all, it is needful for us to make
no distinction of parties in this great undertaking; but of whatever
nation or religion a man be, he ought to be looked upon, if one of us,
to be of the same interest and inclination. We must not act apart in
anything, but in a firm and united body, and distinct from all other
interests whatsoever.’
The design of Paterson presents such indications of a great, an
original, and a liberal mind, as to make the obscurity which rests on
his history much to be regretted. The narrow, grasping, and
monopolising spirit which had hitherto marked the commerce of