Exoemission from Processed Solid Surfaces and Gas Adsorption

238 Pages·2023·10.294 MB·English

by  Yoshihiro Momose

Springer Series in Surface Sciences 73
Yoshihiro Momose
Exoemission
from Processed
Solid Surfaces
and Gas
Adsorption
Springer Series in Surface Sciences
Volume 73
Series Editors
Gerhard Ertl, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany
Hans Lüth, Peter Grünberg Institute, Forschungszentrum Jülich GmbH, Jülich,
Germany
Roberto Car, Department of Chemistry, Princeton University, Princeton, NJ, USA
Mario Agostino Rocca, Dipartimento di Fisica, Università degli Studi di Genova,
Genova, Italy
Hans-Joachim Freund, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin,
Germany
Shuji Hasegawa, Department of Physics, University of Tokyo, Bunkyo-ku, Tokyo,
Japan
This series covers the whole spectrum of surface sciences, including structure and
dynamics of clean and adsorbate-covered surfaces, thin films, basic surface effects,
analytical methods and also the physics and chemistry of interfaces. Written by
leading researchers in the field, the books are intended primarily for researchers in
academia and industry and for graduate students.
Yoshihiro Momose
Exoemission from Processed
Solid Surfaces and Gas
Adsorption
Yoshihiro Momose
Department of Materials Science
Ibaraki University
Hitachi, Japan
ISSN 0931-5195 ISSN 2198-4743 (electronic)
Springer Series in Surface Sciences
ISBN 978-981-19-6947-8 ISBN 978-981-19-6948-5 (eBook)
https://doi.org/10.1007/978-981-19-6948-5
© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
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Preface
The purpose of this book is to introduce readers to the study of electron emission
phenomena of metals and semiconductors, in the context of surfaces excited by
various methods, and corresponding applications to surface chemical technology.
This electron emission substantially differs from well-known types of thermionic
emission (high temperature), photoemission, and field emission (high electric field)
from clean surfaces. Such electron emission has been widely known by nomencla-
ture such as the Kramer effect, exoelectron emission, and exoemission. In this book,
we used exoemission. Exoemission occurs from solid surfaces that are subjected
to various processes and has received substantial attention in industrial fields such
as tribology (friction, wear, and lubrication). Exoemission occurs at low temper-
atures, as measured with a Geiger–Müller (GM) counter. Professor Y. Tamai of
Tohoku University has emphasized the importance of the Kramer effect in the field
of tribology. I have been inspired by his guidance. He was the adviser of my thesis and
a long-term collaborator; we have continued corresponding research. The contents
of this book are based mainly on papers published by my group and collaborators.
This book is an introductory text that is suitable for senior undergraduate and post-
graduate students in physics, chemistry, engineering, and metallurgy. Furthermore,
I have attempted to render the book suitable for scientists and researchers in indus-
trial laboratories, who are interested in the surface properties of solid materials. The
general level of presentation has been kept elementary, with emphasis on the physical
and chemical properties of solids, as well as adsorbed or deposited materials.
Controlling the properties of the surfaces and interfaces of solid materials is
pertinent to the functionality as well as the reliability of the surfaces of solid mate-
rials. Processes at solid surfaces are important in industrial fields such as adhesion,
tribology, catalysis, chemical processes, and corrosion. To achieve such function-
ality and reliability, a solid surface must first be subjected to pretreatments—i.e.,
activated—by various processes. One often performs surface processing of solid
materials (such as metals and semiconductors) by external processes such as (1)
mechanical treatment, (2) thin-film coating, and (3) exposure to ionizing irradiation
(such as ultraviolet light, plasmas, and ion as well as electron beams). These surface
processes are termed excitation. Consequently, one introduces functional groups
v
vi Preface
to the surface, and various types of lattice as well as electronic defects form in the
vicinity of the surface. Furthermore, when placed under production sites after surface
processing, oxygen, water vapor, and other environmental materials adsorb onto the
surface. Engineering researchers must perform careful work to reproducibly impart
the same properties to a surface; further efforts are required to develop technologies
for monitoring surfaces and interfaces that are applicable for industrial use.
After the aforementioned excitation, one usually stimulates the surface of solid
materials by temperature and/or light irradiation and further applies an applied
or accelerating voltage to the surface as well as rubbing the surface with a polymer
rod. Such stimulations are conventionally termed thermally (temperature), optically
or photo (light) stimulated electron emission, and the effect of applied voltage.
Furthermore, we have developed two stimulation methods for photoelectron emis-
sion: thermally assisted and temperature-programmed photoelectron emission; as
well as the method of tribo-stimulated (rubbing) electron emission. Thus, by using
these stimulation methods, we imparted a difference to the electron emission char-
acteristics of the surfaces. In particular, this book reveals the electronic properties of
the processed surfaces under the influence of adsorbed foreign materials.
This book is composed of four parts and 12 chapters: Part I, Introduction, Chap. 1;
Part II, EE Mechanism of Metals Subjected to Adsorption, Chaps. 2–4; Part III,
Outline of Development of EE Research, Chaps. 5–7; and Part IV, TAPE, TPPE,
TriboEE, and XPS Characteristics of Processed Surfaces, Chaps. 8–12. I hope that
those who study the physics and chemistry of metal surfaces, as well as those who
are engaged in science and technology research that is related to metal surfaces, will
use or refer to the results described in this document from various perspectives.
It is a pleasure to dedicate this book to the late Professor Y. Tamai, who inspired
my interest in the subject and with whom I had the privilege of working. I thank my
postgraduate and senior undergraduate students of Department of Materials Science
of Ibaraki University (Hitachi campus), who have assisted me in performing studies
and experiments. I wish to thank Dr. K. Nakayama and Dr. T. Sakurai, with whom I
have collaboratively performed research that is related to exoemission and have given
continued support and valuable comments over many years. I acknowledge Dr. I.
Ohshima, with whom I have conducted research in the field of mechanical treatment
of metallic solids. I also thank Dr. M. Takeuchi and Professor H. Mase, who have
made many useful suggestions about applied physics and electronics and provided
encouragement. I also thank Professor Y. Nishiyama and Professor T. Matsunaga,
with whom I studied surface chemistry in Tamai’s laboratory, and for Dr. S. Mori,
who has given me a lot of information about tribology research. Finally, I thank my
wife Takako Momose for her support and encouragement for this research.
Hitachi, Japan Yoshihiro Momose
Contents
Part I Introduction
1 Surface Phenomena and Exoemission ........................... 3
1.1 Pertinence of Exoemission to Surface Phenomena ............. 3
1.1.1 Involvement in Surface Chemical Technology ......... 3
1.1.2 Work Function and Analysis Methods of Electron
Emission ........................................ 6
1.2 Exoemission Phenomena of Processed Surfaces .............. 9
1.2.1 Importance of Exoemission Studies for Processed
Surfaces ......................................... 9
1.2.2 Historical Background ............................. 10
1.3 Exoemission Measurements of Processed Surfaces ............ 11
1.3.1 External Treatments and Terminology
of Exoemission ................................... 11
1.3.2 Trend of Current Studies ........................... 12
1.3.3 Measurement Apparatus and Surface Cleanliness ...... 14
1.3.4 Origin of Exoemission ............................. 14
References .................................................... 15
Part II EE Mechanism of Metals Subjected to Adsorption
2 EE of Clean Metals: Adsorption of Mainly O and H O
2 2
in the UHV and HV ........................................... 21
2.1 Specification of Practical Surfaces .......................... 21
2.2 Development of Chemiemission ............................ 22
2.3 EE Attributable to Adsorption of Electronegative Gases ........ 26
2.3.1 EE During Oxidation of Cs Films Deposited on Ru .... 31
References .................................................... 33
3 EE from Metal Surfaces Covered with Oxide: Adsorption
of Mainly O and H O and Oxide-Film Thickness ................ 35
2 2
3.1 OSEE Observed in the UHV and HV for Al O /Al ............ 35
2 3
vii
viii Contents
3.2 EE Observed in Air for MgO/Mg, Al O /Al, and NiO/Ni ...... 42
2 3
3.3 EE Observed in Counter Gas for Oxide-Covered Metal
Surfaces of Sn, Al, Fe, Ni, and Cu .......................... 46
References .................................................... 52
4 Effects of Organic Adsorption, Applied Voltage, Light
Irradiation, and Catalytic Activity .............................. 53
4.1 Effect of Adsorption on OSEE from Al ...................... 53
4.2 Effect of AV and Light Intensity on OSEE from Al ............ 56
4.3 Relation Between EE and Catalytic Activity of Ag, Cu,
and Pt .................................................. 62
References .................................................... 64
Part III Outline of Development of EE Research
5 Materials, EE Measurement, and EE Characteristics ............. 69
5.1 EE Measurement Methods and EE Data Analysis Methods ..... 69
5.2 Stimulation by Thermal, Optical, and Tribological
Methods After Excitation .................................. 70
5.3 Nomenclature of EE Categorized by Stimulation Methods ...... 72
References .................................................... 73
6 TSEE Related to Plasma Treatment and Adsorption .............. 75
6.1 Outline of TSEE of Metal Surfaces After Plasma Treatment .... 75
6.2 Effect of Discharge, Adsorption, and Heat Treatment
on TSEE from Metals ..................................... 78
6.2.1 TSEE from Spark-Discharged Fe Surfaces
and Adsorption ................................... 78
6.2.2 TSEE from Oxidized and Plasma-Treated Ni
Surfaces ......................................... 80
6.2.3 TSEE After Electric Discharge Treatment
and Chemical Reduction of Cu Surfaces .............. 85
6.3 TSEE from Glass on Au Surfaces, Au, Ni, Si, and Graphite
Subjected to Plasma Exposure; and XPS Analysis ............. 89
6.3.1 TSEE from Glass Deposited on Au Metal Surfaces .... 89
6.3.2 TSEE from Au and Ni Metal Surfaces to Exposed
to Ar and O Plasma .............................. 92
2
6.3.3 TSEE from Ni Metal Surfaces Exposed to Ar
and O Plasma ................................... 95
2
6.3.4 TSEE from Si Wafer Powder Exposed to Ar Plasma ... 97
6.3.5 TSEE from Graphite Exposed to CF , Ar, and O
4 2
Plasma .......................................... 103
References .................................................... 107
Contents ix
7 Effects of Blasting and Grinding Agents as Well as Cutting
Fluids on TSEE from Mechanically Deformed Surfaces ........... 111
7.1 TSEE from Sandblasted Mild Steel and Ground Sand .......... 111
7.1.1 TSEE from Sandblasted Mild Steel and Adsorption
of Organic Vapors ................................ 111
7.1.2 TSEE from Ground Sand Granules
(Aluminosilicate) and Adsorption of Organic
Vapors .......................................... 112
7.2 EE from Metals and Plastics Blasted or Ground
with Abrasive Agents ..................................... 115
7.2.1 TSEE from Metals Blasted with Silicon Carbide
(SiC) ............................................ 115
7.2.2 EE from Plastics Abraded with Al O and SiC ........ 117
2 3
7.3 TSEE from Metal Surfaces Subjected to Cutting
and Grinding ............................................ 117
7.3.1 TSEE from Al Surfaces Cut with a Tool Steel
and Effect of Cutting Fluids ........................ 117
7.3.2 EE from Metals During Cutting with WC
and Friction ...................................... 126
7.3.3 TSEE Under Light Illumination from Low-Carbon
Steel Surfaces Ground with Al O .................. 127
2 3
References .................................................... 132
Part IV TAPE, TPPE, TriboEE, and XPS Characteristics of
Processed Surfaces
8 TAPE of Rolled and Scratched Fe Metal Surfaces ................ 135
8.1 Temperature Dependence of PE from Rolled Fe Surfaces ....... 135
8.2 Wavelength Dependence of PE from Rolled Fe Surfaces ....... 141
8.3 PE from Practical Fe Surfaces Scratched in Air, Water,
and Organic Liquids ...................................... 148
8.3.1 PE in Temperature Scans of Scratched Fe Surfaces
and XPS Analysis ................................. 148
8.3.2 Activation Energy of PE from Scratched Fe
Surfaces ......................................... 148
8.3.3 PE in Wavelength Scans of Scratched Fe Surfaces ..... 153
8.4 Temperature Analysis of PE and XPS Data of Scratched
Fe Surfaces .............................................. 156
References .................................................... 161
9 TAPE of Si Wafers ............................................ 163
9.1 Effect of Adsorption of O and H OonEEfromSi ........... 163
2 2
9.2 PE from Si Wafers and Activation Energy .................... 165
9.3 PE from Si Wafer Surfaces Implanted with
H, Si, and Ar Ions ........................................ 168
References .................................................... 172