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Plasma Physics
Nonthermal Plasma Nonthermal Plasma

Chemistry and Physics Chemistry and Physics
edited by
In addition to introducing the basics of plasma physics, Nonthermal Plasma
Chemistry and Physics is a comprehensive presentation of recent develop-
Jürgen Meichsner
ments in the rapidly growing field of nonthermal plasma chemistry. The book Martin Schmidt
offers a detailed discussion of the fundamentals of plasma chemical reactions
and modeling, nonthermal plasma sources, relevant diagnostic techniques, Ralf Schneider
and selected applications.
Hans-Erich Wagner
Features
• Includes a compact introduction in the nonthermal plasma

physics and plasma–surface interaction
• Classifies the plasma sources and chemical plasma reactors,
and provides important similarity parameters
• Overviews experimental methods in plasma diagnostics and
surface (thin film) analysis
• Presents detailed research results with modeling and applications
• Promotes strategies in plasma modeling and provides specific
methods, including examples
Elucidating interconnections and trends, the book focuses on basic princi-

ples and illustrations across a broad field of applications. Expert contributors
address environmental aspects of plasma chemistry. The book also includes
selected plasma conditions and specific applications in volume plasma
chemistry and treatment of material surfaces such as plasma etching in
microelectronics, chemical modification of polymer surfaces and deposition
of functional thin films. Designed for students of plasma physics, Nonthermal
Plasma Chemistry and Physics is a concise resource also for specialists
in this and related fields of research.
59165
ISBN: 978-1-4200-5916-8
90000
9 781420 059168
59165_Cover_mech.indd 1 9/28/12 10:20 AM

Nonthermal Plasma
Chemistry and Physics
© 2013 by Taylor & Francis Group, LLC

Nonthermal Plasma
Chemistry and Physics
edited by
Jürgen Meichsner
Martin Schmidt
Ralf Schneider
Hans-Erich Wagner
Boca Raton London New York
CRC Press is an imprint of the

Taylor & Francis Group, an informa business

Cover design by Sascha Meichsner and Carsten Desjardins.
CRC Press
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Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii
Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 2 Nonthermal Plasma Chemical Processes of General Interest . . . . . . . . . . 7
Chapter 3 Physics of Nonthermal Plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Chapter 4 Nonthermal Plasma Chemical Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Chapter 5 Elementary Processes on Surfaces in

Plasma–Wall Interaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
Chapter 6 Plasma Diagnostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Chapter 7 Surface and Thin Film Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
Chapter 8 Selected Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Chapter 9 Modeling and Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
Chapter 10 Trends and New Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539

Preface
Plasma processing is one of the key technologies worldwide, especially using non-
thermal, low-temperature plasmas. Recently, the situation is characterized by the
fast-growing interest in the optimization of existing applications as well as the
development of new ones.
This book provides a basic introduction to nonthermal plasma chemistry and
physics for students of plasma physics, PhD students, and scientists. The fundamen-
tals of plasma chemical reactions and its modeling, most importantly nonthermal
plasma sources, relevant diagnostic techniques, as well as selected applications, are
presented and discussed in a systematic manner. Interconnections are shown; trends
and new concepts are illustrated. The chapters discuss the basic principles and pro-
vide exemplary illustrations of the wide field of applications. Therefore, it is not the
aim of this book to give a complete overview of the state of the art in the research
areas. For this, the readers can refer to already existing excellent monographs and
topical reviews given in the references.
The book is based on contributions from internationally known experts in their
research fields, using examples from their own scientific activities to illustrate the
basic principles with applications.
After a short introduction to the field of nonthermal plasma chemistry with some
historical notes and its specific characteristics, topics of general interest in this field are
briefly presented, which illustrate the broad spectrum of applications. Dry air plasma
chemistry with ozone generation or lacquer stripping and ashing reactions are briefly
discussed. Plasma etching presents a key technology in integrated circuit production.
Methane gas reformation as well as diamond deposition are important topics of
hydrocarbon plasma chemistry. The formation of pre-biochemical compounds is also
observed in nonthermal plasmas. Thin film generation of plasma polymers, of metallic
compounds, and silicone-based cells are products of plasma chemical processes.
The fundamentals, sources, and diagnostics of nonthermal plasmas are discussed
next. The basic concepts of plasma physics for thermal and nonthermal plasmas,
including collisional processes, plasma kinetics, and macroscopic transport equations,
are introduced. Due to the importance of surface processes in many applications, the
plasma-wall boundary is also considered. The basic physics of different nonthermal
plasmas of electric discharges and the realizations for technical plasma sources are
presented at the end of this chapter.
Nonthermal plasma reactors are characterized in terms of the principles of
chemical quasi-equilibria, macroscopic kinetics, and plasma chemical similarity.
Plasma–surface interaction is one of the fastest-growing branches in plasma
physics and has got an important issue in the field of applied surface science. Its basic
question concerns the mastering of an old problem: the contact of different states
of matter. The investigation and application of plasma–surface interaction plays an
essential role in low-temperature plasma processing such as etching, deposition, or
modification of surfaces as well as in fusion research. Therefore, such elementary
processes on surfaces in contact with plasmas are discussed. The particle and energy
balance at the surface determine the importance of the different mechanisms.
vii

viii Preface
According to the broad spectrum of plasma components, different tasks exist

for the investigation of the plasma to understand the processes and to control
chemical reactions characteristic of the various applications. Therefore, the funda-
mentals of probe measurements, microwave interferometry, emission and absorption
spectroscopy, laser-induced fluorescence spectroscopy, and gas chromatography are
discussed.
Complementary techniques needed for surface and thin film analysis are
presented next.
The first part of the next chapter presents examples of applications of volume
plasma chemistry. The reactions take place in the volume, as pure gas phase reac-
tions, or in heterogeneous processes with participation of the surface of substrates,
electrodes, or walls, sometimes assisted by catalytic effects. The second part con-
cerns applications of surface chemistry. Here the plasma chemical reactions result in
changes in surface properties. The reactions may involve volume processes, but the
essential reactions take place at the surface. Etching and thin film deposition as well
as surface functionalization up to plasma medical applications are presented.
Modeling and simulation provide an increasing number of tools to improve the
basic understanding of nonthermal plasmas and allow predictive studies for optimiza-
tion of processes. The hierarchy of plasma models is explained at the beginning of the
next chapter, followed by a discussion of theoretical concepts for elementary volume
and surface processes in gas discharges. The chapter concludes with an example
of modeling, namely, the spatiotemporal dynamics in radio-frequency discharges of
oxygen and its comparison with experimental results.
The book concludes with a discussion of trends and new concepts in this
fascinating and dynamic research area.

Acknowledgments
We would like to express our deep gratitude to all coauthors. They are the fundament
on which this work is based.
A very special thank you goes to Andrea Kleiber (Max-Planck-Institut für Plasma-
physik, Teilinstitut Greifswald, EURATOM Association, Greifswald) for her endless
patience and amazing support. The book would never have been completed with-
out her uncountable contributions and her careful attention. Bert Krames helped as
emergency support in the final processing and transformed the impossible into reality.
We would also like to gratefully acknowledge the work of Marcel Beu (Leibniz-
Institut für Plasmaforschung und Technologie e.V. (INP Greifswald)) for helping us
with the drawings.
This work was partly supported by the Deutsche Forschungsgemeinschaft, Son-
derforschungsbereich Transregio 24. One of the editors (M. S.) appreciates the support
of the INP Greifswald.
Very special thanks go to Lance Wobus of Taylor & Francis Group for his valuable
advice and his patience during the preparation of this book. We gave him a hard time
with this project, but he was always giving us a backup whenever problems appeared.
ix

Editors
Jürgen Meichsner
Institut für Physik der Ernst-Moritz-Arndt-Universität Greifswald, Felix-Hausdorff-
Str. 6, D-17489 Greifswald, Germany
Martin Schmidt
Leibniz-Institut für Plasmaforschung und Technologie e.V. (INP Greifswald) Felix-
Hausdorff-Str. 2, D-17489 Greifswald, Germany
Ralf Schneider
Recent address:
Max-Planck-Institut für Plasmaphysik, Teilinstitut Greifswald, EURATOM Associ-

ation, Wendelsteinstr. 1, D-17491 Greifswald, Germany
Hans-Erich Wagner
xi

Contributors
Name Institute Sections
Kurt H. Becker PU Brooklyna Section 8.3
Ronny Brandenburg INP Greifswaldb Section 8.2.2
Franz X. Bronold IfP Greifswaldc Section 9.2
Paul B. Davies DoC Cambridged Section 6.3
Andreas Dinklage IPP Greifswalde Section 6.4
Kristian Dittmann IfP Greifswaldc Section 9.4
Jörg Ehlbeck INP Greifswaldb Section 8.2.2
Holger Fehske IfP Greifswaldc Section 9.2
Rüdiger Foest INP Greifswaldb Sections 8.2.2 and 8.2.3.4
Mario Hannemann INP Greifswaldb Section 6.1
Hans-Jürgen Hartfuß IPP Greifswalde Section 6.2
Rainer Hippler IfP Greifswaldc Section 8.4
Holger Kersten IEAP Kielf Sections 5 and 8.4
Kirill V. Kozlov MSU Moscowg Section 8.1.1
Boris P. Lavrov FoP St.-Petersburgh Section 6.3
Detlef Loffhagen INP Greifswaldb Sections 8.1.3 and 9.1
Jürgen Meichsner IfP Greifswaldc Chapters 1, 10, Sections 3.1
through 3.7, 7.1
Siegfried Müller INP Greifswaldb Sections 8.1.2, 8.1.3, and
8.2.2.2
Andreas Ohl INP Greifswaldb Section 8.2.3.4
Abha Rai IPP Greifswalde Sections 8.2.4.1.1 and 9.3
Jürgen Röpcke INP Greifswaldb Section 6.3
Antoine Rousseau LPT Palaiseau Cedexi Section 6.3
Martin Schmidt INP Greifswaldb Chapters 1, 6, 10, Sections 3.8,
6.5, 7.3, 8.1, and 8.2
Ralf Schneider IfP Greifswaldc Chapters 1, 4, 10,
Sections 8.2.3.1.1, 9.3, and 9.4
†
Karsten Schröder INP Greifswaldb Sections 7.2 and 8.2.3.4
Hartmut Steffen INP Greifswaldb Sections 7.2 and 8.2.4.2
Dirk Uhrlandt INP Greifswaldb Section 9.1
Achim von Keudell RUB Bochumj Chapter 5
Th. von Woedtke INP Greifswaldb Section 8.2.3.5
Hans-Erich Wagner IfP Greifswaldc Chapters 1, 4, 10, Section 6.6
(continued)
xiii

xiv Contributors
(continued)
Name Institute Sections

K.-D. Weltmann INP Greifswaldb Section 8.2.3.5
Harm Wulff IfB Greifswaldk Sections 7.3, 7.5, and 8.2.4.2
Rolf-Jürgen Zahn INP Greifswaldb Sections 8.1.2 and 8.2.3.3
a
Polytechnic Institute of New York University, Brooklyn, NY 11201, USA.
b
Leibniz-Institut für Plasmaforschung und Technologie e.V. (INP Greifswald), Felix-
Hausdorff-Str. 2, D-17489 Greifswald, Germany.
c
Str. 6, D-17489 Greifswald, Germany.
d
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2
1EW, U.K.
e
Max-Planck-Institut für Plasmaphysik, Teilinstitut Greifswald, EURATOM Associa-
tion, Wendelsteinstr. 1, D-17491 Greifswald, Germany.
f
Institut für Experimentelle und Angewandte Physik der Christian-Albrechts-
Universität zu Kiel, Leibnizstr. 19, D-24118 Kiel, Germany.
g
Moscow State University, Department of Chemistry, 119991 Moscow, Russia.
h
Faculty of Physics, St.-Petersburg State University, Ulianovskaya 2, 198904
St.-Petersburg, Russia.
i
Laboratoire de Physique et Technologie des Plasmas, Ecole Polytechnique, Route de
Saclay, F-91128 Palaiseau Cedex, France.
j
Ruhr-Universität Bochum, Universitätsstraße 150, D-44801 Bochum, Germany.
k
Institut für Biochemie der Ernst-Moritz-Arndt-Universität Greifswald, Felix-
Hausdorff-Str. 4, D-17489 Greifswald, Germany.
†
Deceased.

1 Introduction
CONTENTS
1.1 Plasma Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Historical Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.3 Thermal and Nonthermal Plasma Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4 Specifics of Nonthermal Plasma Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1 PLASMA CHEMISTRY

The plasma state of matter (also named fourth state) is characterized by the exis-
tence of free electrons, positive and negative ions, as well as excited species and
radicals in mixture with the other neutrals of gaseous systems (atoms, molecules) or
liquids. Well-known examples for natural plasmas are the interstellar matter, stars,
the ionosphere, lightnings, and flames.
Plasmas are generated by the input of thermal energy, electric field energy, radi-
ation, or beams (lasers, UV photons, electrons, protons), respectively. The principles
of plasma generation are summarized in Figure 1.1. The focus of the book is on
technical plasmas in gaseous systems that are mostly initiated by applied electric
fields. Examples of such electrical gas discharges are the corona and barrier dis-
charge, sparks, arcs, and plasma torches, operating usually at atmospheric pressure.
Technically important low-pressure plasmas are the different kinds of glow discharges
driven by dc and rf voltages or microwaves.
Gas heating by thermal energy and/or collisions of neutrals with free electrons
and photons of sufficiently high energy initiate the production of free radicals and
further charged species. The generated particles are the source for various chemical
reactions in the volume as well as on the plasma interfaces, forming new compounds,
depositing layers, and modifying the properties of materials.
The science and application of chemical conversions in plasmas, including

reactive processes at interfaces, is the subject of plasma chemistry.
1.2 HISTORICAL NOTES

The existence of chemical reactions in plasmas, initiated by the input of electrical
energy in gaseous atmosphere, is a very old experience of mankind, with even Homer
describing the smell of sulfur∗ in the Iliad in air after lightning.
∗
Sulfur was later identified as nitrogen oxides.

2 Nonthermal Plasma Chemistry and Physics
Radiation
photons Thermal energy
Plasma gas heating
Beams compression
electrons
protons Chemical processes
…
Heating of electrons
Electrical
Electric current in gas
gas discharges
Breakdown
Electric fields
FIGURE 1.1 Principles of plasma generation.
Important historical milestones in the investigation and application of plasma

chemical reactions are as follows:
• The synthesis of H2 O in spark discharges operating in H2 /O2 mixtures

(H. Cavendish 1781)
• The fixation of air nitrogen in spark discharges forming NO
(H. Cavendish 1784, J. Priestley 1785)
• The discovery and application of the ozonizer
(W. v. Siemens 1857)
• The conversion of organic compounds in silent discharges
(M. Berthelot 1866)
• The industrial production of nitrogen oxides in the arc discharge
(Birkeland-Eyde process 1905)
• The industrial production of acetylene in plasmatrons
(Hüls process 1940)
1.3 THERMAL AND NONTHERMAL PLASMA CHEMISTRY

We have to distinguish two kinds of plasma chemical conversions, the thermal as
well as the nonthermal plasma chemistry. In the case of thermal plasma chemistry the
plasmas act primarily as generators of thermal energy. They operate typically in the
kW to MW power range. At high temperatures (range 103 –104 K) and high specific
enthalpies, the chemical compounds are decomposed. This process is called plasma
pyrolysis. The chemical reactions take place in/or nearby the thermal equilibrium,
characterized by the common temperature (the gas temperature) of all species. The
output of reaction products has to be optimized by a quenching procedure and their
separation from the gas mixture.

Introduction 3
(a)
Processes in space
Pel
Active zone Passive zone

Reactants Te >>Tg Te ≈Tg
Stable
products
A1 A1
Hot electrons
A2 A2
Elementary reactions Ak
Dissociation Recombination
Ak excitation, de-excitation,
etc. etc. Al
Pel
Active phase Passive phase

Time τ
Processes in time
(b)
FIGURE 1.2 Operation scheme of a nonthermal plasma chemical flow reactor (a) and of a
closed reactor (b), with Pel electrical power, Te kinetic temperature of electrons, and Tg gas
temperature.
The subject of this book is the plasma chemistry in nonthermal plasmas. In this
case, the reaction mixture is far from the thermal equilibrium. The chemical conver-
sions are initiated by the high temperature (Te ≥ 104 K) of free electrons at relative low
gas temperature (Tg ≤ 103 K) (plasma electrical conversion). The processes take place
under highly nonequilibrium conditions of all plasma species. Hot electrons, ener-
getic ions, cold excited species, free atoms, and radicals are produced in the so-called
active zone (phase) of the different kinds of nonthermal (electrical) gas discharges. In
the passive zone (phase), the electrons cool down fast. The unstable plasma compo-
nents change to stable reaction products by volume and wall reactions. The operation
scheme of nonthermal plasma chemical reactors is illustrated in Figure 1.2.
1.4 SPECIFICS OF NONTHERMAL PLASMA CHEMISTRY

Two important advantages of the application of nonthermal plasma chemistry have
to be emphasized. First, because of the high electron temperature of 104 –105 K

(about 1–10 eV mean energy), reactive processes that require an extremely high
activation energy can be realized. Therefore, nearly all plasma chemical processes
are practicable, including the synthesis of rare and new products. For example,
the effective synthesis of ozone succeeds only under nonthermal plasma conditions.
Second, as a result of the relative low gas temperature, there is no thermal dissociation
of reaction products and no quenching needed. Connected with this, the thermal stress
of the reactor walls as well as of the treated interfaces is minimal. Therefore, thermal-
sensitive materials can only be modified under nonthermal plasma conditions. This
fact was essentially important for the fabrication of microelectronic elements, and it
opens the window for future technical applications, e.g., in plasma medicine.
On the other hand, the selectivity of nonthermal plasma processes, the output,
and energetic efficiency of the reaction products is usually small, with the exception
of ozone synthesis. Therefore, the applications of nonthermal plasma processing are
dominated by reactive plasma-wall processes (modification, etching of targets, thin
film deposition, etc.). Important applications are summarized in Figure 1.3.
Nonthermal plasma chemical flow reactors are often operated under low pressure
conditions. This requires the installation of an expensive vacuum technique and
limits the introduction of plasma processes in technological lines. To overcome these
problems, the recent trend worldwide is to develop atmospheric pressure plasma
methods. The focus is directed on the application of numerous types of microplasmas.
Nonthermal plasma processes take place under highly nonequilibrium conditions
for all species. Therefore, microphysical modeling of the physics and chemistry in
nonthermal plasmas requires the knowledge of the energy distribution function of the
Process Application Industry
Volume chemistry
Ozone synthesis Purification

Air and flue gas cleaning Environmental protection
VUV radiation sources Plasma displays Electronic industry
… … Mechanical engineering
Optical industry
Vehicle construction
Microelectronics Textile industry …
Surface chemistry Micromechanics Printing and packaging industry
Hardening Energy technology
Etching Corrosion protection Plasma medicine
Structuring Wear resistance, wettability …
Cleaning Photovoltaics
Functionalization Biocompatible layers
Thin film deposition Heterogeneous catalysis
… …
FIGURE 1.3 Important applications of nonthermal plasma chemistry.

Introduction 5
electron gas in the active reactor zone. Its simulation has to be solved simultaneously
with the complex system of master equations for heavy particles, including the
reaction products. The mass action law of the equilibrium chemistry is not applicable.
Generally, the solution of this complex problem is a challenge to computational
physics.
The realization and optimization of plasma chemical processes starts with the
selection of suitable plasma sources. Indispensable are a profound plasma diagnostics
and process control. This requires the knowledge of the discharge operation param-
eters (power input, pressure, flow, gas mixture, etc.) and its interconnection with
the most important plasma parameters (gas temperature, electron density, electron
energy, electron distribution, etc.) and the plasma chemical process itself (particle
densities, mass balance, surface properties, etc.).
To sum up, nonthermal plasma sources of technical relevance, important diag-
nostic methods, as well as the fundamentals of kinetic modeling of complex plasma
processes are presented in this book.

2 Nonthermal Plasma
Chemical Processes of
General Interest
CONTENTS
2.1 Dry Air, Oxygen, and Nitrogen Plasma Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.1 Ozone Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.2 Plasma Ashing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2 Plasma Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 Hydrocarbon Plasma Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.1 Methane Gas Reformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.2 Diamond Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3.3 Origin of Prebiochemical Compounds on Earth . . . . . . . . . . . . . . . . . . . . . 12
2.3.4 Plasma Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3.5 Thin Film Deposition of Metal Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4 Thin Film Silicon Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
In this chapter, typical topics of general interest are briefly presented, which illustrate
the broad spectrum of applications. Dry air plasma chemistry with ozone generation or
lacquer stripping and ashing reactions are briefly discussed. Plasma etching presents
a key technology in integrated circuit production. Methane gas reformation as well
as diamond deposition are important topics of hydrocarbon plasma chemistry. The
formation of pre-biochemical compounds is observed in nonthermal plasmas, too.
Thin film generation as plasma polymers, of metallic compounds and silicone-based
cells are products of plasma chemical processes. Detailed discussions of selected
topics are given in Chapter 8.
2.1 DRY AIR, OXYGEN, AND NITROGEN PLASMA CHEMISTRY

The main processes in nonthermal plasmas operating in oxygen, nitrogen, or dry air
plasma are dissociative collisions of molecules, resulting in the generation of the
reactive atoms (O, N) [1,2], the formation of excited atoms and molecules, as well
as positive or negative ions. The formation of negative ions is essential mainly for
electronegative gases such as oxygen. The dissociative attachment of electrons of
excited O2 molecules generates negative atomic ions as well as oxygen atoms. The
threshold energy of this process is essentially lower than electron impact dissociation
and dissociative ionization of ground state molecules [3]. The reaction probability of

e– Air e–
O2 N2
O O2* N N2*
N O2
O2
N O3
O3 NO O2
NO O3 N*
NO2
O3 N
NO3 NO2 N2O
NO2 NO2
NO3
N2O5 N2O4
FIGURE 2.1 Diagram of primary chemical reactions in dry air plasma induced by electron
impact. (According to Becker, K.H. et al., Air plasma chemistry, in Becker, K.H. et al. (eds),
Non-Equilibrium Air Plasmas at Atmospheric Pressure, IoP, Bristol, U.K., pp. 124–182, 2005.)
heavy particle reactions of electronically excited species can exceed the probabilities
of ground state reactions by orders of magnitude [4,5].
The air plasma chemistry, e.g., is responsible for producing Nx Oy compounds,
which have a key role in global environmental problems like acid rain. The scheme
in Figure 2.1 of dominant plasma chemical reactions in dry air demonstrates the
complexity of the processes [6].
The plasma chemistry in oxygen is also of practical importance, namely, for
the ozone generation and for plasma ashing. Augmented combustion is essentially
influenced by air plasma chemistry [7].
2.1.1 OZONE GENERATION

Ozone is a powerful oxidizing agent which is non-chlorine alternative applied for
water treatment, disinfection, and odor removal. The only economical method for
ozone production is by dielectric barrier discharge in atmospheric pressure oxygen
or air with its nonthermal plasma. Ozone is the sole substance which is generated in
volume processes in nonthermal plasma in industrial dimensions.
Ozone results in three-body collision processes
O + O2 + M → O∗3 + M → O3 + M, (2.1)
where M is a third collision partner as O2 , O, also O3 or N2 . Oxygen atoms are gener-

ated by dissociative electron impact. The ozone formation is reduced by competitive
reactions like recombination of two O atoms to O2 or reactions of O atoms with
ozone molecules O + O3 + M → 2O2 + M [8]. In Section 8.1.1 the ozone synthesis
is discussed in more detail.

Nonthermal Plasma Chemical Processes of General Interest 9
2.1.2 PLASMA ASHING

The interaction of an oxygen plasma with hydrocarbon compounds leads to CO2 and
H2 O. In microelectronic industry, e.g., the photoresist mask is removed (stripped)
by an oxygen plasma. Damage of the semiconductor material by high-energy ions
must be avoided by low ion energies and high fluxes of neutral radicals, i.e., oxygen
atoms to the resist surface. The low-temperature plasma ashing procedure is used
for preparation of samples for electron microscopy [9] and for quantitative analysis
of lignite [10]. Oxygen plasmas are applicable to precision cleaning of metallic
surfaces contaminated by organic substances such as grease or oil [11]. Hazardous
gaseous organic molecules as volatile organic compounds (VOCs) may be destroyed
by reactive species like O∗2 (a1 Dg ), O(1 D), O(3 P), H, OH, N∗2 (A3 S+u ), N∗2 (B3 Pg ), and
N best into CO2 or H2 O [12].
2.2 PLASMA ETCHING

Plasma etching is the key technology for patterning in every chip production in
the microelectronic industry. It enables nonisotropic etching in sub-μm range with
significant increasing of packed density of electronic elements in integrated circuits
applied in computer production. For this process a nonreactive gas is fed into the
plasma where it is activated. The interaction of this activated gas with a solid substrate
generates in a chemical reaction a volatile compound which contains atoms of the
substrate. Exemplary is the silicon etching by a fluorine compound feed gas as
CF4 . The plasma activation leads to generation of fluorine atoms by electron impact
dissociation of the CF4 molecule.
CF4 + e− −→ CF3 + F + e− . (2.2)
The fluorine atoms react with silicon and produce volatile SiF↑4
Si + 4F → SiF↑4 . (2.3)
The activation energy for desorption of the etch product SiF↑4 is transferred from the
plasma to the surface by ion bombardment. Because of the existence of fluorocarbon
radicals (CFn ) a polymer film is deposited on the silicon surface, also on sidewalls
of trenches. The sidewall protection is important for the anisotropy of trench etching
with high aspect ratio (ratio depth to width).
Fundamental starting processes of activating the etching gases are the electron–
molecule collisions. A critical review of data of electron collision processes for a lot
of fluorine and chlorine containing gases is given by Christophorou and Olthoff [13].
An extensive presentation of plasma etching can be found in Section 8.2.1.
2.3 HYDROCARBON PLASMA CHEMISTRY

Important reaction channels in hydrocarbons are induced by collisions of hot electrons
with gaseous molecules in a cold environment. It offers a broad spectrum of appli-
cations beyond standard organic chemistry. The spectrum covers from complicated

reactions of the formation of bio-organic compounds in the early earth atmosphere,

natural gas reformation, thin polymeric film formation, and creation of higher hydro-
carbons to deposition of diamond-like thin films and generation of pure carbon as
soot or even diamond.
2.3.1 METHANE GAS REFORMATION

Methane is a dominant part of natural gas. Other sources are petroleum processing
off-gas and biogas. It is an important energy carrier and initial compound of chemical
industry but also a dangerous greenhouse gas. Electron impact dissociation leads to
CH3 radicals and H atoms [14]
CH4 + e− −→ CH3 + H + e− . (2.4)
Another pathway is the reaction of this molecule with hydrogen atoms (also generated
by electron impact processes) [17]
CH4 + H −→ CH3 + H2 . (2.5)
The abstraction of further H atoms leading to CH2 , CH, and C is possible by H atoms
but also by electron collisions, especially in pure methane plasmas. The reverse
reaction, the addition of H atom to CH3 to form CH4 occurs at low temperature
[18]. H atoms may be generated by dissociative electron collisions of H2 molecules;
at higher gas temperatures thermal dissociation of hydrogen molecules becomes
dominant as studied in thermal plasma chemistry. Here, some processes may be more
effective, but the specific production sensitivity of nonthermal plasma chemistry is
lost due to generation of new compounds in a cold gaseous environment.
A reaction scheme is presented in Figure 2.2 for dissociative electron collisions
with CH4 and H2 molecules [15] as well as for the formation of CHx and C2 Hy
compounds controlled by collisions of hydrocarbon molecules with H atoms [16].
Concerning the variety of the processes in a H2 –CH4 plasma, including the electron
impact-induced reactions, see also [15].
The principle process scheme (see Figure 2.2) shows the formation of ethane,
ethylene, and acetylene. An investigation of methane conversion in a pulsed
microwave discharge (p = 30 mbar) yields a selectivity of acetylene generation near
70% with an energy input of 10 eV/molecule. Here the methane dissociation is
initiated by electron impact. The generated H atoms provide the source for further H
atom abstraction from the methane molecule [19].
The conversion of a CH4 /CO2 mixture into higher hydrocarbons or syngas
(CO/H2 ) in a hybrid catalytic plasma reactor is reviewed by Istadi [20]. The chemical
reactions are initiated by electron impact dissociation of CO2 and CH4 generating CO
and O as well as CH3 and H, respectively. An important research topic is the direct
conversion of methane and carbon dioxide to methanol [21,22]. The investigation of
the reaction products of methane–CO2 mixture in an atmospheric pressure dielectric
barrier discharge shows a small concentration of methanol, but a lot of other pure

CH4 H2
+e− +e−
CH3 CH2 CH 2H
+H +(H,H2) +(H,H2)
CH4 C2H6
+ M) +H(−H2)
+H(−H2) (CH 3 +H+M
+H+M
(M) C2H5
CH3 +H(−H2)
+H+M
C2H4
+H(−H2)
+H(−H2)
+H+M
CH2 C2H3
+H(−H2)
+H(−H2) +H+M
C2H2
CH +H(−H2)
C2H
+H(−H2)
+H(−H2)
C C2
FIGURE 2.2 Reaction schemes for the electron collision of CH4 induced CH3 , CH4 , and
CH formation. (According to Röpcke, J. et al., J. Phys. D: Appl. Phys., 34, 2336, 2001.) H2
dissociation and of the transformation of C1 Hx and C2 Hy species by reactions with H atoms in
diamond plasma CVD. (According to Ma, J. et al., Exploration of the gas phase chemistry in
microwave activated diamond depositing plasmas by laser spectroscopy, in ISPC 2007 Peking
CD, ISPC, Peaking University, Beijing, China, 2007.) M indicates the action of the wall.
and oxygenated hydrocarbons. A carbon chain growth is supposed to occur mainly

by the reaction
Cn H2n+2 + CH4 → Cn+1 H2n+4 + H2 . (2.6)
According to the practical application an essential problem is the bad selectivity

of the plasma process [22,23]. Products of the methane conversion include syngas,
gaseous products as ethylene, acetylene, and propylene, liquid hydrocarbons, plasma
polymers, and oxygenates. The complexity of hydrocarbon plasmas is demonstrated
in [24] by review of plasma chemical reactions in low-pressure acetylene plasmas.
A spectacular example of application of nonequilibrium plasma chemistry is the
deposition of diamond films.

2.3.2 DIAMOND DEPOSITION

Plasma-assisted chemical vapor deposition enables the formation of diamond at
moderate temperature and low pressure with hydrocarbons as starting compounds on
non-diamond substrates. This allows the extended industrial use of the outstanding
properties of the diamond, such as extreme hardness, high thermal conductivity,
broad optical transparency (deep UV to far IR), and wide band gap (5.4 eV). In gas
phase chemistry of a CH4 /H2 plasma the CH4 molecule is activated which leads to
carbon deposition with sp3 (diamond) or sp2 (graphite) bonding. The hydrogen atoms
generated in the plasma etch the deposited carbon producing volatile compounds CHn
(n = 1 − 4). Because the approximately 100 times higher etch rate of graphite [25]
diamond remains on the substrate.
For the diamond synthesis the principle growth species are CH3 , C2 , and H [26].
In the conventional H2 rich plasma in H2 /CH4 mixtures the CH3 radical is responsible
for the diamond growth. In plasmas with lower H2 concentration, as in Ar/H2 /CH4
gas mixtures C2 controls the diamond deposition.
The radicals C2 , CH, H, CH3 are observed by tunable infrared diode laser
absorption and emission spectroscopy, respectively [16,27].
The impact of the H atoms is manifold for the diamond deposition process.
Besides the already mentioned etching of the graphite phase and the importance for
CH3 generation the H atoms act with bonded hydrogen and create reactive sites for
the reaction of CH3 radicals and serve for the addition of a C atom into the diamond
lattice [26].
Hot filament chemical vapor deposition process and microwave plasma CVD
with low or higher energy input were the most successfully applied methods for dia-
mond deposition [25]. High substrate temperatures (typically >700◦ C) ensure good
diamond quality. For various industrially important applications such as deposition on
microelectronic substrates lower substrate temperatures are necessary. The decrease
of the deposition rate with decreasing substrate temperature could be compensated
using other starting gases such as halogenated compounds like C2 H5 Cl [28] or CO
[29] and CO2 [30] with H2 admixtures.
The deposition of well-ordered nanostructures as nanotips and nanotubes,
nanowalls, graphene, and ultra nanocrystalline diamond is also observed under plasma
conditions using as source material mixtures of carbon-carrier gases such as hydro-
carbons, fluorocarbons, etc. [31–35]. Fullerenes are generated successfully in thermal
plasmas [31].
A more detailed discussion of the plasma-assisted deposition of a-CH films,
diamond and erosion of graphite by H atoms is given in Section 8.2.4.1.1.
2.3.3 ORIGIN OF PREBIOCHEMICAL COMPOUNDS ON EARTH

One exciting and still not resolved question is the origin and the development of
life on earth. The first step may be the formation of organic molecules, e.g., amino
acids. Miller [36] investigated spark discharges in a mixture of methane, ammonia,
hydrogen, water vapor, and liquid water. In particular, under the action of UV radiation
the formation of various organic compounds were observed, e.g., hydrogen cyanide,
amines, aldehydes, acrylonitrile. In the aqueous solution, amino acids were formed.

The products in the gas phase were generated by reactions between free radicals
and ions.
The state of the early earth atmosphere is discussed by Abelson [37]. An N2 –
CO–H2 atmosphere is supposed and HCN and H2 O were the principal products of a
gas discharge, beside small amounts of CO2 and CH4 . HCN in aqueous solution can
lead to other organic compounds.
Also the plasma chemistry in CH2 –H2 S [38] and CH4 –PH3 [39] atmospheres is
studied to detect prebiochemical substances.
These experiments show the formation of organic compounds in plasma chemical
experiments, but the further reaction steps in the direction of formation of living
structures are largely speculative.
2.3.4 PLASMA POLYMERIZATION

Plasma polymerization is a process of thin film deposition on electrodes, walls, or
substrates under the action of plasmas in an organic molecules containing atmosphere.
The term “polymerization” is misleading because this product is not a polymer
consisting of equal components. Plasma polymer films consist of highly cross-linked,
brittle material with good dielectric properties. They are pinhole-free, have low sol-
ubility, pronounced chemical inertness, and good adhesion to the surface. A broad
spectrum of organic compounds such as hydrocarbons, fluorocarbon, and silicon
organics was applied for plasma polymerization. In contrary to chemical polymeriza-
tion these starting compounds in the feed gas can be free of double or multiple bonds
or cyclic structures. The starting gas is activated in the plasma by electron collisions
or by collisions with other energetic plasma components as H atoms. Ionic or neutral
radicals are created. The target surface is activated by ion bombardment. The radicals
diffuse (neutral) or drift (ionic) to the surface where they are bonded to the surface.
The starting material can also move directly to the surface where a plasma-induced
polymerization is possible.
Section 8.2.4.1.2 gives more detailed information on plasma polymerization.
2.3.5 THIN FILM DEPOSITION OF METAL COMPOUNDS

A method of thin film deposition of simple metal compounds (e.g., oxides, nitrides)
is the plasma-enhanced chemical vapor deposition with metal organic starting gases.
The advantage of this method is the low substrate temperature and is therefore useful
for deposition on temperature sensitive materials [40]. A study of deposition of TiN
using Tetrakis(diethylamine)titanium (TDEAT) shows the importance of H-radicals
in the H2 plasma for the stripping of TDEAT. The formation of TiN requires N2
addition to the process [41].
The deposition of thin films of pure metals or simple metal compounds is possible
by sputtering in low-pressure discharges inert gas. An example of reactive sputtering
is the deposition of TiN films. The nitride formation is a surface process of the freshly
deposited Ti with plasma-activated nitrogen.
Plasma-enhanced atomic layer deposition (PEALD) of metals or metallic com-
pounds is based on a sequential use of self-terminating plasma-enhanced gas solid

reactions which leads to a coverage of the target surface by monolayer films with
good conformality [42].
2.4 THIN FILM SILICON SOLAR CELLS

The development of alternative energy sources to adverse fossil fuels is an important
task for science and technology in the twenty first century. Photovoltaic is a promising
candidate in future renewable energy technology. Thin Si-films are expected to be
successful material for effective solar cells [43,44]. Beside other methods plasma-
enhanced chemical vapor deposition is widely used for generation of amorphous
silicon (a-Si:H) and microcrystalline (μc-Si:H) films. Feed gas for plasma-assisted
silicon deposition is mainly pure monosilane SiH4 or SiH4 /H2 mixtures. Inside the
plasma silane is dissociated by electron impact into SiH3 , SiH2 , SiH, Si, H2 and H,
and H2 in H atoms. Also SiH+x , SiH−x , and H+x ions are generated. Secondary ion
molecule reactions and reactions between neutral species also have to be taken into
account, too. Data on silane plasma chemistry are reviewed in [45].
SiH3 reaching the surface reacts to SiH4 with bonded hydrogen atoms and
generates dangling bonds or recombines with another SiH3 to Si2 H6 . SiH4 and
Si2 H6 are desorbed from the surface. The formation of a Si–Si bond occurs by
reaction of SiH3 radicals with dangling bonds, the Si film is growing [43]. The
low-temperature plasma-enhanced deposition process (150◦ C–300◦ C) enables the
deposition on temperature-sensitive substrates as polymer foils. The fabrication of
homogenous large-area a-Si:H films with high deposition rate is important for applica-
tions from an economical viewpoint. Parallel plate rf-reactors operating at 13.56 MHz
are usually used. Deposition rates of 0.2–0.3 nm/s are observed. Rates of 2 nm/s were
achieved by higher operating frequency (70 MHz). The deposition rate of μc-Si:H
could be increased by application of a narrow gap discharge at higher pressures [46].
2.5 SUMMARY
Selected examples of the various possibilities of plasma chemical processes were
presented. Most applications concern surface processes, such as thin film deposi-
tion, etching, and cleaning. Only one volume process for the generation of larger
amounts of material has reached technical maturity and commercial importance, the
ozone synthesis. Some processes and procedures are specific for plasma processing.
Examples are the micropatterning in microelectronics, or the deposition of plasma
polymers on various substrates.
The aim of future technical developments must be to enhance the selectivity
and energy efficiency of plasma chemical processes, and research may lead to new
materials with exciting properties.

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in this street are evidently much older than those of Eglinton Street.
The site of the first premises of the U.C.B.S. is now covered by a part
of the Coliseum theatre. Here, in this small place, the modest
beginning was made on the morning of 26th January 1869. One is
curious as to the quantity turned out in this first baking, but that is a
matter on which all records are silent. Occasionally we are told of the
purchase of flour and of the price which was paid for it, but for some
time no mention is made of the quantity baked into bread. At that
time the secretary was a very busy man. Not only was he during these
first few months virtual manager of the bakery, but he was also the
manager of the S.C.W.S., and he had his hands full of work.
Although the minutes are silent on some phases of the work of the
committee, however, they are prolix enough on others. The wages of
the vanman are given, and at the same meeting—that of 6th February
—we are told that the wages of the foreman baker were fixed at 34/ a
week. It was also agreed at the same meeting that the bread be sold
at current retail price and that a discount of 10 per cent. be given.
Three weeks later the need for a larger van was being discussed, and
at the next meeting, held a week later, it was decided that a Parkhead
van-builder be given the order to build a van large enough to contain
fifty dozen loaves; and that another horse be purchased. A shop in
connection with the bakery had now been opened, and it was decided
that the shop hours should be from eight a.m. until seven p.m. The
question of a weekly half-holiday, presumably for the girl in the
bread shop, was also considered, but allowed to lie over. From the
next minute it becomes evident that the committee’s idea of the class
of horse which was required for the work of the Society had
undergone some change during their month’s experience, for
whereas the first horse which they purchased cost £18, they paid £40
for the next one.
At the beginning of the month the hours of the shop girl had been
fixed at from eight to seven, but on the 27th of the same month an
alteration was made, and it was agreed that the shop should open at
7·30 in the morning and remain open until 7·30 at night. On
Mondays it was to be shut at 5 p.m. and on Saturdays to remain open
until 9 p.m., while the price of bread was fixed at 5½d. The
committee were now finding that they required stable and van room
more than they had available, and agreed to advertise for it.
Evidently the shop girl found the 7.30 a.m. start too early for her, for
at a meeting of the committee held a fortnight after the earlier
opening of the shop had been decided on, the minute records that
she should “be spoken to about attending at her hour in the
morning.”
DIFFICULTIES BEGIN.
By this time the members of the committee were beginning to
realise that there were difficulties in running a baking business.
Complaints had been made that the bread was sour, and the foreman
baker laid the blame on a change of temperature. The explanation
was quite likely to be the correct one, although a foreman with an
interest in his work might have been expected to take precautions
against such difficulties. The committee were not long in discovering
that this was just what their foreman did not do. At the next meeting
his attention was again called to complaints about the bread. This
time it was being sent out to the shops in a dirty condition. He was
also informed that the blend of flours which he was using was costing
too much, and the committee decided that they should draft a
statement of the proportions in which the differently priced flours
were to be used. It was also decided to dismiss one of the vanmen on
the ground that he was careless about his work and his horse.
In the case of the baker matters went from bad to worse until, an
earlier historian[1] tells us, he struck work altogether. The committee
for some time had been in constant fear that some morning the
ovens would be found cold, or else that the bread would be burnt
black, and the crisis came when, at 11 p.m. one Thursday toward the
end of May, the president was aroused from sleep to receive the
intelligence that the Baking Society had given up business. This was
serious news; but sure enough, when he had hurriedly dressed
himself and made his way with all speed to Coburg Street, he found
the bakery in darkness. Mr Borrowman was next awakened, and told
the doleful tidings. Both gentlemen hurried to the foreman’s house to
discover that happy-go-lucky individual soundly asleep, careless that
hungry Co-operators would be breadless in the morning. He was
induced to go to work, and next day the committee were hastily
summoned, only to discover that the foreman was tired of his job,
and had fully made up his mind that he was going to be responsible
no longer for supplying Co-operators with the staff of life. The
committee were at their wits end, but there was nothing for it but to
get another baker. Here the minutes take up the story. The
committee at their meeting spoke to the foreman about the loss on
the first quarter’s working, which amounted to £37. His reply was to
the effect that he never expected to make a profit the first quarter.
They then spoke to him of the numerous complaints which were
being received with reference to the quality of the bread, and he
replied that as he was unable to do better the best thing he could do
was to resign. His resignation was accepted, and after very
considerable difficulty another man was found to take his place; but
he only remained a week or two, and ultimately, in June, another
man was procured who was able to do better. No balance-sheet was
printed for any of the quarters in the first year, but a written
statement, showing the position of the Society, was sent to each
member. The first quarterly meeting was held on 29th May, when
the rules were adopted. Mr Gabriel Thomson was elected president;
Mr John West (St Rollox Society), treasurer; Mr James Borrowman
(Anderston Society), secretary; and Messrs James Ferguson
(Barrhead), Joseph Gibb (Thornliebank), Alexander Douglas
(Anderston), and Weir (Motherwell) as committee. It was also agreed
that the secretary be paid £1, 10s. and the treasurer £2 quarterly.
1. The United Co-operative Society Year Book, 1896.
With the appointment of a new foreman the bakery was now
running more smoothly than during the first quarter, but it was not
yet paying its way, for the minute of 29th June records the fact that
the loss at that date was £25. The explanation of this position, as
given by the secretary, was that a liability of £4, 15s. had not been
taken into account at the last balance, some flour which had been
bought had not been used when the price fell, and this had entailed a
loss of £6, 10s. An encouraging feature, however, was a report given
by the new foreman which showed that a profit had been made in
each of the two weeks with which it dealt. The sales were also rising,
but the committee were not satisfied with the trade the Society was
doing, and were desirous that the turnover should be raised to sixty
sacks or seventy sacks a week, as they thought that with such a
turnover they would have a good profit. As a preliminary step to
securing this turnover they determined to send out several of their
number as missionaries to societies which had not yet joined, with
the object of getting them to do so, or, at least, to purchase their
bread from the Society. Amongst other minor difficulties with which
the committee were being faced at this time was the lack of suitable
stabling for their horses. Their stable was too small, and it was
unhealthy. It is true that horses were not very costly, but neither was
money too plentiful, and they could not afford to run any risks. One
of the horses which they had bought in the beginning of the year was
ill, and had to be sold for £6. A decline of £12 in the value of a horse
inside a few months was evidence that there was something wrong
somewhere, but suitable stabling was difficult to secure.
A MANAGER APPOINTED.
In the minutes the most important things sometimes crop up in
the most casual manner. At a meeting of the committee which was
held on 18th September, one of the principal themes of the evening’s
discussion was the purchasing of new horses. A horse was to be
returned as unsuitable, and another horse priced at £30 was to be
taken on trial, as it would not suit the committee that anything
should be paid to the owner as “rue bargain.” Then, quite casually,
the minute goes on to mention that “the engaging of Mr Sturrock as
manager of the Baking Society was then gone into.” This is the first
mention made in the minutes of the proposal to appoint a manager;
but, from the document which had been prepared and which was
transcribed into the minute of the meeting, it is evident that the
subject had been under consideration for some time. It is interesting
to note in this agreement that “the manager was not to exceed 3/ for
baking and firing.” He was to determine “the quality and also the
maker’s flour he shall use, but the committee reserve the right to
prevent the price of flour used any week exceeding the average price
of extra flour.” He was to keep the accounts of the Society, and
prepare weekly statements which would give
“the number of sacks baked and also the cost of the flour and other
materials, wages, rent, cost of horse-keep, etc., giving the total of the whole,
with a statement of the number of loaves baked from each sack, the total
number of dozens of loaves produced, with smallbread; also the cash value of
the loaves and smallbread added and the expense with the cost deducted,
showing clear profit; also a statement showing the number of dozens of loaves
and smallbread sent to each society, with the number left on hand at the end
of each week.”
The pay of the manager was fixed at 35/ per week until the Society
was able to pay a bonus of sixpence per £, when his wages were to be
advanced to 40/ per week.
Already the directors were beginning to find that if it was difficult
to sell as much bread as they desired, it was equally difficult
sometimes to get payment for the bread they did sell. There was
hardly one of the Glasgow societies but had to struggle hard to keep
going at all. Of all those societies in the city to which the new venture
must look for its best support there were not more than two which
emerged safely from the struggles of those early days, and those two
survived only because the men in charge of them refused to recognise
defeat and kept going even against the advice of the friends who
foresaw in a longer struggle but greater disaster. Of the eight
societies which had joined in the formation of the Federation only
two were pursuing smoothly the even tenor of their way, free from
the irritating worries produced by the difficulty of making ends meet.
These two societies—Thornliebank and Barrhead—were associated
with the Bakery from the very first meeting, and being successful
they were in a position to pay their way promptly; but some of the
others were not so fortunate, and so, in October of the first year, we
find the manager being instructed by the committee to write to the
societies and point out to them that as the capital was limited it
would be an advantage if payment was made promptly when the
accounts were rendered. Frequently during the next few years the
same complaint crops up, and there were times when the Society was
owing the S.C.W.S. large sums of money which at the moment it was
quite unable to pay because of the fact that the societies were not
paying promptly for the goods they received.
The third quarterly meeting took place on 4th December. Although
there is nothing about it in earlier minutes, a hint is given that the
committee or the manager had not been keeping to the strict line of
instructions given at the August quarterly meeting, for a motion is
agreed to “that the alteration in the price of bread take place on the
same day as the Glasgow prices.” A profit had been made on the
quarter’s transactions, but it was not large enough to divide, and the
delegates gave authority to the committee “to apply it to redeem
fixed stock.” About this time the Society was having trouble with the
quality of flour purchased. The flour was returned, and the manager
was authorised to cancel the order if that sent in exchange was not of
better quality. The committee at the close of their first year were
discussing the necessity of getting more ovens, as the old bakery was
quite inadequate to meet the trade which was being done. It was
agreed to endeavour to get other two ovens; and, failing that solution
of the difficulty, to see if a nightshift could be employed. Later
minutes are silent as to how the difficulty was overcome during the
three months which elapsed ere the new bakery in St James Street,
Kinning Park, was ready for occupation.
SOMETHING ATTEMPTED, SOMETHING
DONE.
During the first year the committee had been feeling their way.
They had met and overcome many difficulties, some of which, like
the incident of the chairman and secretary hunting up a recalcitrant
baker in the small hours of the morning in order to induce him to go
to work, have a humorous enough aspect when viewed at a distance
of fifty years, but must have seemed tragic to the actors, for the
whole future of the infant venture would seem bound up in an
unbroken sequence of bread deliveries. For the first year the
committee met in the premises of the S.C.W.S. in Madeira Court.
Usually the meeting place was the warehouse, for the room in which
Mr Borrowman worked was but small, although it possessed the only
window in the place. There they fitted up a temporary table, using
boxes for seats. Indeed, so long as Mr Borrowman continued
secretary of the Baking Society, the committee continued to meet
frequently in the Wholesale’s premises, although the sub-committee
usually met in a small room, 10 ft. by 6 ft., fitted up in the bakery
premises at St James Street. At times the full committee of sixteen
met here also, packed together like herrings. Such were the
conditions to which those heroes of the Co-operative vanguard
accommodated themselves in order that the cause they had at heart
might prosper.
During the first year the Society had baked 2,116 sacks of flour,
equivalent to an average turnover of 40¾ sacks per week; but as the
turnover during the latter part of the year was approximately 70
sacks per week, it must have been much less than 40 at the
beginning. For the first six months losses amounting to £62, 10s. had
been made, but in the second six months these losses had been
wiped out, the fittings had been depreciated by over £30, and
although no dividend was declared they had a balance of surplus to
carry forward which amounted to £23, 3s. 1d. The value of the goods
sold during the year had been £5,081, 13s. 6d.; the value of the fixed
and live stock was £243, 15s. 8d.; and the value of their building, as
shown in the balance-sheet, £110, 9s. 6d. The societies held share
capital amounting to £193, 12s. and loan capital amounting to £145,
and £10, 6s. 1d. had been paid as interest. Thus the position was
quite good. The corner had been turned; a surplus was being shown
most weeks, and the directors were assured that with careful nursing
and a steady influx of trade prosperity was in sight. Many rocky
headlands had yet to be weathered, many shoals avoided, adverse
winds and tides overcome, ere their bark reached the wide open sea
of prosperity; but the mariners were shrewd and careful, and
although for one reason and another several changes of captain and
even of crew took place, the new crews and the new captains sailed
their ship always with the skill of the old and, successfully
overcoming all difficulties, were at last wafted by fair winds over a
smooth sea.
CHAPTER IV.
ST JAMES STREET BAKERY.
A HINDRANCE TO THE PROGRESS OF THE SOCIETY—THE

SEARCH FOR NEW PREMISES—THE NEW BAKERY—
RUNNING INTO DEBT—THE CHAIRMAN RETIRES—MORE
CAPITAL WANTED—SLOW PROGRESS—THE MANAGER
RESIGNS—JOINING THE WHOLESALE SOCIETY—
PAYMENT OF BONUS COMMENCED—MR BARCLAY
RESIGNS—ADDITIONAL PROPERTY PURCHASED—MR
CAMERON RESIGNS—MR ANDREW BROWN BECOMES
CHAIRMAN—BAD BREAD AND DELIVERY DIFFICULTIES—
FURTHER EXTENSIONS—MONEY DIFFICULTIES—MR
BORROWMAN RETIRES—BECOMING BISCUIT AGENTS.
Long before the end of the first year of their tenancy of Coburg
Street bakery the committee had come to the conclusion that if their
business was to grow and flourish they must remove to more suitable
premises at the earliest possible moment. As one of themselves put
it, they discussed “the present bakery as a hindrance to the progress
of the Society.” The result of this discussion was that a circular was
issued to the societies, in which the committee recommended the
building of a new bakery. During the months of October and
November 1869 the question was discussed on several occasions, and
at least two special meetings of the committee were held for its
consideration. At the second of these, held on 6th November, a sub-
committee was appointed to look out for a site, and a week later it
was decided to write to Mr M‘Kay, of Alva, asking his advice on the
subject. There is no doubt that the matter was urgent. The trade was
growing rapidly, and there were numerous complaints regarding late
delivery of bread. The subject crops up in the minutes again and
again, and the manager is unable to get out enough bread early in the
day to meet the demand.
Still, the committee are cautious. They have now discovered that
the Society can be made a success; they have also gained some
knowledge of the difficulties which are to be encountered; and so,
not content with applying to the Alva Baking Society for information,
they also get into communication with the Dunfermline Baking
Society, and receive a letter in which that society’s bakery is
described. Meantime, the sub-committee appointed to look out for a
site had not been idle. They had discovered a building at the corner
of St James Street and Park Street, Kinning Park, which was for sale,
and which they thought could be so altered as to make suitable
premises for the Society and, after due consideration doubtless and
careful inspection, although the minutes are silent on the subject, the
matter was brought before the December quarterly meeting and
purchase was approved of, provided the cost was not more than
£400.
THE NEW PREMISES.
The building was purchased at once, and steps were immediately
taken to have it fitted up as a bakery. It was decided to erect four
ovens at an estimated cost of £210 for the four, while a part of the
building was fitted up as a stable. To-day, the fitting up of a bakery of
this size would seem quite a small matter and not at all a thing to
make a fuss over, but it is easy, nevertheless, to imagine the loving
care with which those old veterans watched the transformation
which was taking place; how they deliberated over the merits of
asphalte as a satisfactory material for the floor, and the utility of
cast-iron fittings as against wooden ones for the stable. The manager
made a special journey to Irvine to arrange at the quarry there for
proper stones for the oven soles, what time the sub-committee were
arranging to get estimates for tables and troughs for the bakery. By
the end of January the manager was able to announce that the stable
was finished, and was instructed to employ a man to take charge of it
and attend to the horses. At the same meeting it was agreed that the
S.C.W.S. be allowed stabling for a horse and van, and that they pay a
fair share of the expenses. Already, too, the new bakery was so far
advanced towards completion that the committee had begun to
consider the question of having a formal opening ceremony, and a
supper, to which it was proposed that “two or three members of the
committee of each society within easy distance should be invited,
whether they were members or not.”
By the middle of March the manager was in a position to state that
the bakery “would be ready for business in two or three weeks’ time
at most.” At the same time it was decided to erect a house for the
manager on the property, the rent of the house to be considered
later. At the same meeting the committee had a visit from Mr
Keyden, writer, who stated that he had learned that the Society were
desirous of raising a loan on their property, and had called to find
out what the amount was and what rate of interest they were willing
to pay. The secretary stated that the amount would be from £400 to
£500, and the rate of interest 4½ per cent. per annum. At a later
meeting the question of the opening celebrations was again
considered, when, amongst other decisions arrived at, was one to the
effect that two gallons of “drink,” presumably whisky, should be
procured for the use of those who attended. It was agreed that
invitations be sent to societies who were members and to others
within a convenient distance, also to the employees of the Society,
past members of the committee, Mr M‘Kenzie, of the P.C.M.S., Mr
Marshall S.C.W.S., and such Wholesale Society directors as lived
within a suitable distance for attending. The decision about the
whisky evidently did not find favour with some people, for at the next
meeting of the committee the matter was again under consideration,
“and after mature deliberation it was then agreed to have none, as
the committee had been informed that there were many objections to
the same.” In the beginning of May the new bakery was opened for
business.
But in thus following up the negotiations about the new premises,
we have been running ahead. The fourth quarterly meeting was held
on 19th February 1870, when some important changes were made in
the method of conducting the business. For the first year each society
which was a member of the Federation had a representative on the
committee, and this arrangement was continued by resolution of the
quarterly meeting. The whole committee resigned in order that it
might be reconstructed, and Mr Thomson was re-elected to preside
over the business of the meeting. Some of the regulations drafted
that afternoon are amusing. It was decided that each member of
committee receive one shilling for every meeting of the committee
which he attended, along with travelling expenses; but it was also
decided that any member of the committee who was later in arriving
at a committee meeting than fifteen minutes after the time fixed for
the meeting should not only forfeit his allowance for attending, but
should also, unless reasonable excuse was shown, be fined sixpence
for being late. What was to happen if a member did not attend at all
was not stated, but no member of the committee was to be paid his
allowance unless he was present at the meeting.
THE CHAIRMAN RETIRES.
A large number of changes were made in the personnel of the
committee at this meeting. Mr Gabriel Thomson retired from the
presidency, and Mr William Barclay, also of St Rollox at that time,
was elected president in his stead. The other members of committee
were Messrs Ferguson, Barrhead; Gibb, Thornliebank; John
Borrowman, Anderston; Kinniburgh, Cadder; Mungall, Cathcart; and
Shaw, Lennoxtown; with Mr James Borrowman still secretary. At
this meeting exception was taken to the propaganda activities of the
committee, for a letter from Paisley Equitable Society was read to the
meeting in which the Society was charged with trying to injure that
society’s trade with the Provident Society, and the secretary was
instructed to reply denying that such had been the policy of the
Society. It was also from that quarterly meeting that the proposal
came that a house should be built for the manager in the new
premises, in order that he might have the premises under his
supervision at all times.
MORE CAPITAL WANTED.
As the Society, at the end of the first year, had only a paid-up
capital amounting to £338, all of which was locked up in stock,
fixtures, etc., it was evident that they required much more if they
were to finance their larger venture. The visit of Mr Keyden has
already been referred to, and ultimately a bond on the property was
taken up through him, but the committee were desirous of securing
capital also from the societies. These were written to by the manager,
requesting them to increase the amount of loan capital they had with
the Society, and by the middle of April six societies had increased
their loans by an aggregate amount of £275.
M‘NEIL STREET PREMISES (1897–1903).

CLYDEBANK BAKERY
The insurance on the new premises was fixed at £1,000, divided

into £400 on stock, £300 on the buildings, and £300 on horses and
vans. For several years the Society continued to suffer from lack of
capital, however, and it was not until it had been in existence for
nearly ten years that the committee ceased to be troubled with
financial worries. On several occasions appeals were made to the
delegates attending the quarterly meetings that they would bring
under the notice of their societies the urgent need of the Baking
Society for more capital, and for several years a system of receiving
loans from private depositors was adopted, but this system was
stopped, except in the case of employees, when the Federation began
to receive enough capital from the societies to meet its needs.
SLOW PROGRESS.
The difficulty which arose from shortage of capital was not the
only one with which the committee was faced, unfortunately.
Foreman baker after foreman baker was tried, but still complaints of
the poor quality of the bread continued to pour in. Added to this
there were the difficulties of delivery. When the Co-operators of to-
day see the vans of the U.C.B.S. arriving at the various shops with the
regularity of clockwork, they may have some difficulty in realising
that fifty years ago the problem of prompt delivery was a very serious
one, and one which engaged the attention of management and
committee almost continuously for several years. In part, this was
due to the fact that the baking of bread had not been reduced in
those days to a state of scientific accuracy, as it is to-day, and partly it
was due to the shortcomings of the human element, which has
always a tendency toward failure at the most unexpected times and
often in the most unexpected ways. The craze for new bread was as
great fifty years ago as it is to-day, but the difficulty of delivering it
was very much greater, and it was especially great in the earlier years
of the Baking Society’s existence because of the fact that the majority
of the societies in the outer area supplied by the Federation were but
small and could give but small orders, thus increasing the cost of
delivery until sometimes it transformed trade which should have
been profitable into a losing business.
So much so was this the case that, in the first two or three years,
society after society, which had joined the Federation and were
anxious to trade with it, had to be asked to withdraw because the cost
of delivery was so great that it could only be done at a loss to the
Federation. The first societies to suffer in this way were Motherwell
and Dalziel. At a later date, Vale of Leven Society, which had been
having their bread sent by rail, had to withdraw, and later still,
Lennoxtown were asked to make arrangements for getting bread
elsewhere as soon as possible, on the ground that the Baking Society
was losing eleven shillings every week through delivering bread to
them by van.
As time went on, too, the position was becoming more and more
difficult for the manager. He does not seem to have been a strong
man, or else he had grown careless. At all events, at one quarterly
meeting when the criticisms of the delegates had been even more
searching than usual, he left the meeting before its close, and when
the committee adjourned to the committee room at the close of the
meeting they found a letter from him intimating his resignation.
Whether it was with the idea of getting a little of his own back, or
because he thought that having engaged the employees it was his
duty to dismiss them is unknown, but when he took his own
departure he also dismissed the office and breadroom staffs, and
there was a little difficulty for a day or two until they were brought
back or others procured in their places. After discussion, the
committee decided that they would not advertise for a manager, but
for a confidential clerk and cashier, and Mr Robert Craig, then
bookkeeper with the S.C.W.S., was the successful applicant.
The trade was increasing slowly but steadily, and during the
second year averaged 90 sacks per week. Shortly after the removal to
the new bakery the Society had four vans on the road, and was
supplying eleven societies. In June of that year it was decided to take
up thirty shares in the S.C.W.S., and pay one shilling per share, but a
month later this decision was departed from in favour of one that the
question of joining the Wholesale Society be left to the quarterly
meeting. This decision had its origin most probably in the fact that
the Society had no money to spare at the moment for investment, as
at the same meeting it was decided that the manager make an effort
to pay the flour merchant and take flour into stock.
At the quarterly meeting it was decided that the Society should
join the S.C.W.S., and take up two shares for every society which was
a member of the Federation. At the same time, the members of the
committee were becoming more confident in their handling of the
business, one evidence of this being the fact that they were
purchasing flour in much larger quantities. The new bakery had only
been in operation for six months when the trade had increased so
much that the erection of other two ovens was being considered, and
at the same time the reroofing of a shed for the purpose of turning it
into a flour store was agreed on, and the manager was instructed to
“get estimates of the cost of having the floor laid with any material
that would keep out rats.” It would appear, however, that the cost
was more than the committee could venture to face at the moment,
and it was not until the following April that the question of new
ovens was again raised, when all the societies were written to on the
subject and all agreed to the proposal of the committee.
Meantime the second year had ended with the position of the
Society improving. The sales had amounted to over £9,000, and a
dividend of sixpence had been paid each quarter. Stock and buildings
were valued at £1,370, while the members held £279 in share capital
and £709 in loans. The nucleus of a reserve fund had been formed,
and the property of the Society had been depreciated by £150. It is
interesting to note also that with the beginning of the second year the
Society had begun to pay bonus on wages, a practice which has
continued without intermission ever since. The beginning was
humble—the amount paid in this first year was only £20, 17s.—but it
marked the recognition of the principle that the worker was
something more than a mere hireling; that he was a being who had
something to do with the making of profits, and therefore had a right
to share in them.
The committee continued unremitting in their attempts to extend
the trade of the Society. Every complaint was inquired into closely,
and every little while a deputation was sent to one or other of the
societies with the view of inducing them to become members or to
extend their trade. It is interesting to note also that the cost of flour,
which had been 31/ in May 1869, had advanced to 41/ in April 1871.
The first quarter of the third year was a decidedly successful one, as
it showed a surplus over cost which enabled a dividend of one
shilling per pound of sales to be declared. The membership had
increased to 14, and the turnover to 102 sacks per week, an increase
of 11 sacks per week in one quarter. At the end of this quarter Mr
Barclay retired from the presidency, after having held that position
for fifteen months, and Mr Donald Cameron, Thornliebank, was
elected to the chair. At the following quarterly meeting it was agreed
that, in future, tickets, with a programme of business for the
quarterly meeting, be sent to the societies.
Before the end of the year a building in Park Street, adjoining the
Society’s premises, came on the market, and was purchased by the
Society for £735. At the same time the building of other two ovens

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Nonthermal Plasma Chemistry and

Physics 1st Edition Jurgen Meichsner

Introduction to Plasma Physics 1st Edition Gerard

Fundamentals of Plasma Physics Fourth Edition

Thermal and Nonthermal Encapsulation Methods 1st

Introduction to Plasma Physics With Space Laboratory

Basic Sciences in Ophthalmology Physics and Chemistry

Laser Experiments for Chemistry and Physics 1st Edition

Plasma and Thermal Spraying 1st Edition Juraj Ružbarský

Emerging Thermal and Nonthermal Technologies in Food

Nonthermal Plasma Nonthermal Plasma

• Includes a compact introduction in the nonthermal plasma

Elucidating interconnections and trends, the book focuses on basic princi-

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Boca Raton London New York

CRC Press is an imprint of the

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No claim to original U.S. Government works

International Standard Book Number-13: 978-1-4200-5921-2 (eBook - PDF)

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Chapter 2 Nonthermal Plasma Chemical Processes of General Interest . . . . . . . . . . 7

Chapter 3 Physics of Nonthermal Plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Chapter 4 Nonthermal Plasma Chemical Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137

Chapter 5 Elementary Processes on Surfaces in

Chapter 6 Plasma Diagnostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187

Chapter 7 Surface and Thin Film Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

Chapter 8 Selected Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285

Chapter 9 Modeling and Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407

Chapter 10 Trends and New Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

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According to the broad spectrum of plasma components, different tasks exist

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Max-Planck-Institut für Plasmaphysik, Teilinstitut Greifswald, EURATOM Associ-

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Name Institute Sections

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1.1 PLASMA CHEMISTRY

The science and application of chemical conversions in plasmas, including

1.2 HISTORICAL NOTES

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FIGURE 1.1 Principles of plasma generation.

Important historical milestones in the investigation and application of plasma

• The synthesis of H2 O in spark discharges operating in H2 /O2 mixtures

1.3 THERMAL AND NONTHERMAL PLASMA CHEMISTRY

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Active zone Passive zone

Active phase Passive phase

1.4 SPECIFICS OF NONTHERMAL PLASMA CHEMISTRY

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Process Application Industry

Ozone synthesis Purification

FIGURE 1.3 Important applications of nonthermal plasma chemistry.

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2.1 DRY AIR, OXYGEN, AND NITROGEN PLASMA CHEMISTRY

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2.1.1 OZONE GENERATION

where M is a third collision partner as O2 , O, also O3 or N2 . Oxygen atoms are gener-

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