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PHD Dissertation Jorge Sanchez (For Print)
PHD Dissertation Jorge Sanchez (For Print)
博士學位論文
以超臨界氬氣電鍍製作銅金屬薄膜
及材料分析之研究
Study on the Fabrication of Copper Metal
Coatings by Electroplating Under Supercritical
Argon and Material Characterization
研究生:Jorge E. Sánchez
指導教授:莊賀喬 博士
中 華 民 國 108 年 02 月
0
0
摘 要
論文名稱:以超臨界氬氣電鍍製作銅金屬薄膜及材料分析之研究 頁數:
116
校所別:國立臺北科技大學製造科技研究所
畢業時間:一百零七學年度 第一學期 學位:博士
研究生:何仁德
指導教授:莊賀喬博士
關鍵詞:銅金屬電鍍,超臨界氬氣,晶粒細化,參數優化,材料分析,
超音波攪拌
本研究探討在高壓超臨界氬氣(sc-Ar)環境且無添加劑的狀態下進行銅金屬電鍍
製程,所提出電鍍法之可行性及由參數調整判斷最好的電鍍品質。本研究進行
依不同電鍍法形成之鍍膜性質分析,如表面形貌、表面粗糙度、鍍膜硬度、晶
格結構及大小、微應變和內應力等機械性質;電流效率和電導率等電性質;以
及腐蝕行為。為了比較電鍍效果,鍍膜也是由一般傳統電鍍和超臨界二氧化碳
(sc-CO2) 製成;sc-CO2 在超臨界電鍍領域是一種比較常見的溶液。另外,有開
發一個應用於超臨界電鍍的超音波攪拌方法,並與其他所討論的電鍍方法結果
進行比較。
Sc-CO2 電鍍法產生鍍膜晶粒最明顯的細化效果:根據 Hall-Petch 關係,此效果
會改善大部分的機械性質,但也會增加鍍膜的電阻值和殘留內應力。本研究所
提出的 sc-Ar 電鍍技術產生了更溫和的晶粒細化效果;同時得到優於傳統電鍍的
特性,如更快的電鍍速率和改善機械性質。另外,也得到優於 sc-CO2 電鍍的優
點,如較低的電阻值和殘留內應力。
從參數分析得知,當使用我們的電鍍設備進行實驗,sc-Ar 需要的壓力比 sc-CO2
需要的壓力還高 (2500 psi vs. 2000 psi)。根據現有的文獻,當陰極上的擴散層
和分散相之物理尺寸接近,晶粒細化的效果就更明顯,電鍍的品質亦更好。
由於氬氣的凡得瓦半徑大於二氧化碳的凡得瓦半徑,因此 sc-Ar 應該需要較高的
壓力才能接近於擴散層厚度以及達到改善晶粒細化的效果。另外,sc-Ar 製程最
佳化溫度低於 sc-CO2 的最佳化溫度 (35°C vs. 50 °C);我們認為是因為溫度會
主動地改變鍍液的 pH 值和影響到氫析出反應 (hydrogen evolution reaction),以
i
及鍍液中的溶解物質流動性。使用的電流密度也會影響到電鍍法和氫析出反應
在本研究電流密度 5 A/dm2 達到最高的電流效率 (~93%),確定為最佳參數。此
電鍍法產生最小之晶粒尺寸為~ 26 nm。
最後,在 sc-Ar 電鍍法加入超音波(US)攪拌 (頻率:42 kHz,功率:15 W,功率
密度:0.094 W/cm3) 可有效的達到乳化效果,增加金屬離子的流動性。此電鍍
法可產生具有更細的晶粒,更密集的結構和更美觀的樣貌;得到最小的晶粒尺
寸為~ 23 nm。此電鍍法製作鍍膜的機械性質和腐蝕行為優於一般傳統和靜態
sc-Ar 電鍍法。另外,經由超音波攪拌的清潔作用,超音波超臨界電鍍法的電流
效率亦會提高。
ii
ABSTRACT
iii
According to the existing literature, when physical size of diffusion layer and
dispersed phase are similar, grain refinement was more prominent and electroplating
effect was optimal. Because van der Waals radius of Ar is larger than that of CO 2, it
required a higher pressure to approximate diffusion layer thickness and achieve better
grain refinement effect. Moreover, best temperature was lower for sc-Ar than that for
sc-CO2 (respectively, 35°C vs. 50°C); this was attributed to the changes pH and
density that influence the hydrogen evolution reaction and mobility of dissolved
species in the electrolyte. The applied current density also influenced electroplating
process and hydrogen evolution. The best current density was determined at 5 A/dm2,
achieving the highest current efficiency measured (~93%). The smallest grain size
achieved by this process was ~26 nm.
Finally, the addition of ultrasonic (US) agitation (frequency: 42 kHz, power: 15 W,
power density: 0.094 W/cm3) to the sc-Ar electroplating was expected to achieve
emulsification effect, resulting in accelerated metal ion mobility, achieving more
densely-packed structures with even finer grains and a better aesthetic finish. The
smallest grain size achieved by this process was ~23 nm. The resulting mechanical
properties and corrosion behavior of coatings were better compared to those produced
by conventional or silent sc-Ar processes. Moreover, the current efficiency of the
electroplating process was enhanced due to the cleaning effect provided by ultrasonic
agitation in this case.
iv
ACKNOWLEDGEMENTS
During the past five and a half years of my life I have not only been working to obtain
an advanced degree in grad school, but also formed relationships that will last a life
time. First and foremost thanks to my dear family: Juan, Iveth, Joanna, Ines and Kelly,
who gave me their unconditional understanding, love and support through it all. Los
amo familia, al fin lo logré y ¡éste triunfo es para todos!
To my advisor Prof. Ho-Chiao Chuang, who always pushed me to be better, taught me
good work ethic and to whom I owe what I have today; thank you for looking out for
me always!
To Prof. Chun-Ying Lee, whose guidance kept me on the right path whenever Prof.
Chuang or I got lost in research.
To prof. S.T. Huang, Prof. C.R. Yang, Dr. K.Y. Lee and Prof. V. Mani for all their
help and insight during my oral defense.
To my classmates 貫益, 丞祥, 皓雲, 翔云, 愷佑, 允廷, 浚誥; to my seniors 益瑞, 威
宏, 昱璨, 坤憲, 俊元, 光輝, 錫閔, 崇華, 潘博; and juniors 羽傑, 冠霖, 宗達, 惇盛,
懷恩, 承鑫, 晧智, 哲浩, 冠緯, 洺凱 and to all the other students in lab 711-1, lab 320
and lab 613-B for all their direct or indirect help through all this time.
To my friends Carlos F., Christian, Daniel, Enoc, Frank, Isaias, Jose R., Josuet, Olvin
and Marco, thank you for all the advice, encouragement and beers along the way.
To the team at the department of Mechanical Engineering, Taipei Tech, and Graduate
Institute of Manufacturing Technology, Taipei Tech, for taking such good care of me
since my days as an undergrad student.
To anybody else that I should’ve mentioned and didn’t, I am sorry and thank you
anyway!
And finally to my beloved Isabel, gracias por estar conmigo y aguantarme mis locuras
durante todo éste tiempo. Los 3 meses se nos hicieron 4 años, y con fé, toda una vida.
v
TABLE OF CONTENTS
摘 要.............................................................................................................................i
ABSTRACT.................................................................................................................iii
ACKNOWLEDGEMENTS..........................................................................................v
TABLE OF CONTENTS.............................................................................................vi
LIST OF TABLES.........................................................................................................ix
LIST OF FIGURES........................................................................................................x
1.1 Introduction...........................................................................................................1
1.2 Motivation.............................................................................................................2
2.1 Introduction..............................................................................................................4
Chapter 3 Experimentation...........................................................................................18
3.1 Introduction.........................................................................................................18
vi
3.3 Material Characterization...................................................................................25
3.3.4 Hardness.................................................................................................30
4.1 Introduction............................................................................................................40
5.1 Introduction............................................................................................................53
vii
5.8 Parametric Internal Stress Analyses.......................................................................69
6.1 Introduction............................................................................................................77
7.1 Conclusions............................................................................................................95
LIST OF PUBLICATIONS..........................................................................................99
REFERENCES...........................................................................................................102
VITA...........................................................................................................................116
viii
LIST OF TABLES
ix
LIST OF FIGURES
x
Figure 3- 14: (a) Settings of circular arc function used and (b) example of fitted plot in
SigmaPlot software....................................................................................34
Figure 3- 15: (a) Simplified schematic diagram and (b) actual experimental setup of
internal stress measurement in this dissertation........................................34
Figure 3- 16: (a) Simplified schematics, (b) actual experimental setup and (c) probe
geometry of 4P measurement in this dissertation......................................35
Figure 3- 17: Polarization curve under Tafel behavior.................................................37
Figure 3- 18: (a) simple schematic diagram, and (b) actual equipment image of the
PPS setup used in this work: (A) working electrode, (B) reference
electrode, (C) auxiliary electrode, (D) potentiostat...................................39
YFigure 4- 1: SEM images of coating surfaces produced by: conventional
electroplating at (a) low and (b) high resolution; sc-Ar electroplating at (c)
low and, (d) high resolution; sc-CO2 electroplating at (e) low and, (f) high
resolution...43
Figure 4- 2: SEM images of coatings produced by (a) conventional, (b) sc-Ar and, (c)
sc-CO2 electroplating processes................................................................44
Figure 4- 3: XRD peaks obtained from coatings produced in the feasibility stage.....45
Figure 4- 4: Average grain sizes of the coatings produced in this feasibility stage.....46
Figure 4- 5: Average Ra values of coatings produced in this feasibility stage.............47
Figure 4- 6: Average hardness of the coatings produced in this feasibility stage........48
Figure 4- 7: Internal stresses measured from coatings produced in this feasibility
stage...........................................................................................................48
Figure 4- 8: Resistivities measured from coatings produced in the comparative study.
...................................................................................................................49
Figure 4- 9: Current efficiencies calculated from processes discussed in the
comparative study......................................................................................50
Figure 4- 10: Gas release observed from electrolyte: (a) electrolyte before
electroplating, (b) right after electroplating, and (c) after storing for 12
hours..........................................................................................................52
YFigure 5- 1: SEM images of coatings produced by sc-Ar electroplating at 2500 psi, 7
A/dm2. Surfaces produced at: (a) 35°C, (b) 45°C, (c) 55°C; cross-sectional
views of coatings produced at (d) 35°C, (e) 45°C, (f) 55°C…………....56
Figure 5- 2: Changes in electrolyte pH observed in this dissertation under (a) open
atmospheres and (b) pressurized environment..........................................57
xi
Figure 5- 3: SEM images of surface morphologies produced by sc-Ar electroplating at
35°C, 5 A/dm2, and 1100 psi at (a) low and (b) high magnification; 1500
psi at (c) low and (d) high magnification; 2000 psi at (e) low and (f) high
magnification; and 2500 psi at (g) low and (h) high magnification..........59
Figure 5- 4: SEM images of surface morphologies produced by sc-Ar electroplating at
35°C, 1100 psi, and 1 A/dm2 at (a) low and (b) high magnification; 3
A/dm2 at (c) low and (d) high magnification; 5 A/dm2 at (e) low and (f)
high magnification; and 7 A/dm2 at (g) low and (h) high magnification.. 62
Figure 5- 5: XRD spectra of coatings fabricated at 35°C and (a) 1100 psi, (b) 1500 psi,
(c) 2000 psi, (d) 2500 psi...........................................................................64
Figure 5- 6: XRD spectra of coatings fabricated at 45°C and (a) 1100 psi, (b) 1500 psi,
(c) 2000 psi, (d) 2500 psi...........................................................................65
Figure 5- 7: XRD spectra of coatings fabricated at 55°C and (a) 1100 psi, (b) 1500 psi,
(c) 2000 psi, (d) 2500 psi...........................................................................66
Figure 5- 8: Grain sizes calculated from the fabricated coatings in this dissertation for
(a) 35°C, (b) 45°C and (c) 55°C processes................................................67
Figure 5- 9: Average hardness values of coatings fabricated for (a) 35°C, (b) 45°C and
(c) 55°C processes.....................................................................................68
Figure 5- 10: Average Ra of coatings fabricated in this dissertation for (a) 35°C, (b)
45°C and (c) 55°C processes.....................................................................69
Figure 5- 11: Internal stresses calculated from the fabricated coatings in this
dissertation for (a) 35°C, (b) 45°C and (c) 55°C processes......................70
Figure 5- 12: Resistivities calculated in this dissertation for (a) 35°C, (b) 45°C and (c)
55°C processes..........................................................................................71
Figure 5- 13: Current efficiencies calculated in this dissertation for (a) 35°C, (b) 45°C
and (c) 55°C processes..............................................................................72
Figure 5- 14: Tafel plots measured at 35°C (a) 1100 psi, (b) 1500 psi, (c) 2000 psi, (d)
2500 psi.....................................................................................................74
Figure 5- 15: Tafel plots measured at 45°C (a) 1100 psi, (b) 1500 psi, (c) 2000 psi, (d)
2500 psi.....................................................................................................75
Figure 5- 16: Tafel plots measured at 55°C (a) 1100 psi, (b) 1500 psi, (c) 2000 psi, (d)
2500 psi.....................................................................................................76
YFigure 6- 1: Simple schematic diagram of ultrasound cavitation
phenomena…………78
xii
Figure 6- 2: Actual images of (a) ultrasonic horn with controller module, (b)
piezoelectric transducer, and (c) piezoelectric controller module.............79
Figure 6- 3: Example of ultrasonic induced cavitation by (a) ultrasonic horn and (b)
piezoelectric transducers bath...................................................................80
Figure 6- 4: Simple schematics of the ultrasound assisted supercritical electroplating
process.......................................................................................................82
Figure 6- 5: Simplified schematics of the localized anode-cathode reaction under (a)
conventional process and (b) ultrasound assisted supercritical process....83
Figure 6- 6: Actual image of the reaction beaker with piezoelectric transducer
attached......................................................................................................84
Figure 6- 7: Ultrasound-assisted supercritical electroplating equipment schematics. (a)
DC power supply, (b) pressurized reaction chamber, (c) magnetic agitation
plate, (d) hot water circulator, (e) cool water circulator, (f) high pressure
pump + heat exchanger module, (g) ultrasonic controller, (h) air
compressor, (i) gas tank, (T) thermostat, (P) pressure indicators, (V)
pressure valves..........................................................................................85
Figure 6- 8: Actual image of the US-sc electroplating equipment used in this work.. 85
Figure 6- 9: Cross-sectional morphologies of coatings obtained by (a) conventional
process, (b) sc-Ar process, (c) US-sc-Ar process, (d) US-sc-Ar process (at
higher magnification)................................................................................87
Figure 6- 10: (a) Diffraction peaks and (b) microstructural parameters obtained from
XRD analysis of coatings produced..........................................................89
Figure 6- 11: Hardness values measured from Cu coatings produced in this stage.....90
Figure 6- 12: Surface roughness values measured from Cu coatings produced in this
stage...........................................................................................................91
Figure 6- 13: Internal stresses measured from Cu coatings produced in this stage.....92
Figure 6- 14: Electrical properties of Cu coatings produced in this stage. (a) Current
efficiency, and (b) resistivity.....................................................................93
Figure 6- 15: Electrochemical properties of coatings produced by the three
electroplating methods discussed. (a) Open circuit potentials, and (b)
Polarization curves....................................................................................94
xiii
Chapter 1 Introduction and Overview
1.1 Introduction
Material science is the study about the relationship that exists between the structures
of materials to the performance and characteristics obtained. Material science
combines elements of pure physics, chemistry and engineering, which are applied to
understand the material properties and learn how to tune them. Material science is a
very important field which has been integrated into all facets of our modern
livelihood. Applications are endless, and thus better materials are always undergoing
research to enhance housing and architecture, building materials, health and medicine,
transportation, food science and packaging, textiles and clothing, manufacturing,
electronics, etc.
The electronics industry is very important in our technologically inclined society.
Many advancements in the field depend on development of new fabrication methods
or enhancements to existing ones. One of the most popular fabrication methods in the
electronics industry is the electrochemical deposition, also known as electroplating. In
its simplest form, electroplating refers to the process of depositing a coherent metal
coating by passing an electric current to reduce metal cations onto a conductive
substrate. Sometimes this will be aided by the introduction of additives (such as
levelers, accelerators, brighteners, saccharin, etc.), or surfactants to promote
emulsification. Some of the early uses of electroplating were such as decoration
purposes, such as gold coatings over less precious metals for jewelry, or to increase
corrosion resistance of metals, such as nickel coatings over marine hardware.
In the last 20 plus years, there have been abundant advancements to the field of
electroplating, specifically by emulsification of the conductive electrolyte with
supercritical (sc) fluids. The research in supercritical fluids has been extensive since
they were first observed in the late 1800’s. Many applications in diverse fields such as
chemical extraction, carbon capture, chemical decomposition, color dyeing, cleaning,
power generation, refrigeration, as well as electro-less and electrochemical deposition
processes have been developed. The supercritical fluid – enabled deposition processes
focused on carbon dioxide (CO2) reported by Sone et al. have helped speed up many
developments in the field; electroplating under emulsified sc-CO 2 electrolyte can
1
result in enhanced coating properties due mainly to grain refinement. These
enhancements are very attractive and warrant more research in the topic.
1.2 Motivation
2
popular material for electronic devices in semiconductor industry. Characterization of
mechanical and electrical properties was performed and the results from both
supercritical methods were compared to each other and also compared to results
obtained from traditional electroplating.
The contents of this dissertation have been organized in different chapters as follows:
Chapter 1: the introduction delineates the aim of this dissertation and the main
goals pursued as well as a schedule of the work are presented.
Chapter 2: deals with an overview of Cu metal, basics of electrodeposition, the
theoretical concepts related to the basics of supercritical fluids, supercritical
electrodeposition as well as the physical and chemical properties of
nanocrystalline metallic coatings. All sections are accompanied by relevant
literature.
Chapter 3: focusses on the material preparation, electrodeposition setup and
the experimental conditions used to produce the metal coatings under
supercritical electroplating process. The various analyses techniques
considered for this dissertation are described.
Chapter 4: discusses the feasibility of electroplating experimental conditions
used to produce the metal coatings focused exclusively under supercritical
argon environment. Additionally, properties of the coatings prepared by
supercritical CO2 and conventional electroplating processes were compared in
order to assess feasibility of the proposed sc-Ar process.
Chapter 5: discusses parametric adjustments and the effects of fabrication
parameters such as temperature, pressure and current density over the
mechanical, electrical and corrosion performance of the metal coatings.
Chapter 6: presents the novel ultrasound-assisted supercritical argon
electroplating for fabrication of copper coatings. The effects of applied
acoustic energy, cavitation implosions, as well as their influence over coating
deposition and “soft cavitation” under pressurized supercritical environment
are briefly discussed.
Chapter 7: summarizes the main conclusions of this dissertation, as well as
briefly outline suggestions for future work.
3
Chapter 2 Background and Literature Review
2.1 Introduction
This work presents the properties and characterization of copper metal coatings
produced by direct current electrochemical deposition in a commercially available
copper sulfate bath electrolyte enhanced with supercritical fluid solvent. Experiments
were performed in order to understand the effects of various electrodeposition
parameters and electrolyte characteristics affect the physical properties of the
deposited coating. The purpose of this section is to provide the necessary background
on these topics.
Moreover, the background of supercritical fluids in general, supercritical CO 2 in
particular, later exchanging it for supercritical Ar and the development of ultrasound-
assisted supercritical electroplating process.
Copper is a chemical element with chemical symbol Cu and atomic number 29. It is a
very important engineering material due to its high ductility as well as its excellent
thermal and electrical conductivities. Its properties and relevance have been under
scrutiny since ancient times. Copper is used in many fields and has many applications,
such as building material (copper piping, roofing beams for household use; sections of
the statue of liberty in NY, USA), sensing material (strain gauges; thermocouples),
jewelry (copper alloying into sterling silver), currency (coins, ancient ingots and
modern coins), tools (since Egyptian times used in chisels and saws to form rocks for
building pyramids), etc. Demand for copper has been steadily growing in the past 10
years. According to a recent statistic, total global copper production from mines was
estimated at 19.7 million metric tons in the year 2017 [6]. Major producers were
South American countries such as Chile and Peru, as well as China. In a smaller scale,
copper usage in Taiwan market can be divided as shown in figure 2-1 [7]; although
4
data is relatively old, it still displays that the trend is increasing towards electronic
sector.
Copper is one of the few metals that occurs naturally in directly usable metallic forms.
Copper is indispensable to all living organisms because it is a key component in
enzymes important to breathing; it is also present as the blue pigment in certain
species of crustaceans; it is also present in human livers, muscles and bones. Bulk
copper usually displays low hardness due to its weak metallic bonds dominated by its
single s-orbital electron; however its crystal structure can be easily manipulated, so
purposely introducing lattice defects is not uncommon to increase material hardness.
In fact, in this research grain size of copper coatings is purposely refined to
specifically increase coatings hardness, amongst other benefits. Although copper does
not reacts with water, it does reacts with oxygen to readily form copper oxide,
effectively passivating the surface.
There are many copper alloys known in the current literature, with plenty important
engineering applications. Such an example is bronze, which is an alloy of copper and
tin, discovered around 3500 BC; brass is an alloy of copper and zinc; sterling silver is
an alloy of copper and silver; cupronickel which is an important alloy of copper and
nickel, etc.
5
The most common copper compound encountered in the lab is the copper (II) sulfate
pentahydrate (CuSO4 • 5H2O), used in many application such as fungicide, herbicide;
dehydrating agent; water-resistant agent in concretes; chemical tests such as blood
testing for anemia, reducing or non-reducing sugars (Fehling’s solution test); and as
pigment in glass work and in some types of fireworks. Perhaps the most meaningful
use to us is as reaction agent in the electrolyte used in this work; it will be discussed
in more detail in subsequent sections. Some technical properties of copper are
compiled in table 2-1 [8]. Because of the wide use in industrial use and its importance
in electronics, semiconductor industry, study on copper electroplating was topic for
this dissertation.
6
piece or a block of the same metal (M) to be deposited on the work. Both components
are immersed in the aqueous solution called the electrolyte containing one or more
dissolved metal salts as well as other ions that enhance the flow of electricity and
metal ions (Mn+), inside it. In this case, “n” denotes the number of electrons involved
in the reaction. A power supply provides a direct current to the anode, oxidizing the
metal atoms that it comprises and allowing them to dissolve in the solution. At the
cathode, the dissolved Mn+ in the electrolyte solution are reduced at the interface
between the electrolyte and the cathode, such that they deposit onto the cathode. In
this manner, the ions in the electrolyte solution are continuously replenished by the
anode. At first, one of these reactions can occur faster than the other, because of the
varying catalysis or due to work’s surface properties [9]. The whole process is
colloquially known as “redox” and is divided into two separate reactions. The main
reaction, referred to as “oxidation”, releases electrons into solution; and the secondary
reaction is called “reduction” which consumes electrons. The main redox reactions
occurring at anode and cathode for the specific case of Cu are listed in table 2-2. For
the specific case of copper electroplating, copper metal is used as the anode and the
electrolyte solution contains an ion of copper (usually Cu2+) that is desired to be
deposited. Copper dissolves into solution at the anode while it is plated at the cathode.
A constant concentration of Cu2+ is desired in the electrolyte solution. Finally, simple
schematics of electrolytic cell describing redox are shown in figure 2-2.
7
Figure 2- : Simple schematics of electroplating process.
The rate at which the anode is dissolved is equal to the rate at which the cathode is
plated, which can be calculated by Faraday’s Laws of Electrolysis [10]. From these
relationships we know that the quantity of chemical change produced by an electrical
current is proportional to the quantity of electricity that actually passes through, i.e. by
measuring the quantity of electricity passing through the metal coating we can
calculate the expected amount of chemical change produced. Therefore current
efficiency of the fabrication processes in this study can be calculated by Faraday’s
Laws as equation 1 below:
Wactual
CE 100%
Wtheory
, (1)
where CE is the calculated current efficiency; Wactual is the weight actually deposited
on the substrate and Wtheory is the theoretical weight to be expected at 100% efficiency.
The initial weight was subtracted from the actual final weight to find the weight of the
deposited metal coating, and this value was compared to the Wtheory calculated
beforehand, by using the equation 2 shown below.
I t
Wtheory
nF , (2)
8
where I is the electric current applied; t is the electroplating time; µ is the weight of
one mole of the metal; n is the number of electrons transferred by the ion into solution
(which varies for each metal); and F is Faraday’s constant, known to be 96485 C.
Current density is also an important unit used in this work, defined as shown in
equation 3:
I
CD
A (3)
9
Louis Georges Gouy and David Leonard Chapman in the 1910s.
Cu ions exist in the bulk electrolyte as hydrated ions. Under discharge in an electric
field, Cu ions were transported towards the cathode surface; moreover, water
molecules aligned in the diffusion layer, which were then removed in the HDL. When
in Cu ions contact the cathode surface, they discharged and adsorbed at the cathode
surface as ad-atoms. Ad-atoms diffuse in the cathode surface and incorporate into the
crystal lattice at the growth point. The crystal growth mechanism in simple salt
solutions is shown in figure 2-4 below [12].
10
2.4 Fundamental Properties of Supercritical Fluids
Supercritical fluids have been under extensive study in recent years due to their
enhanced physical properties which combine advantages of liquid and gaseous phases
of materials. They display no surface tension because they are not subject to the gas-
liquid boundary, so no molecules have attraction to the inside of the fluid. The term
“supercritical fluid” is attributed to any substance at a temperature and pressure above
a certain temperature and pressure specific to that substance, called critical point.
Above this critical point, the distinct liquid and gas phases do not exist. A regular
pressure-temperature (P-T) phase diagram is shown in figure 2-5 [13]; a visual
example of transformation of subcritical fluid to supercritical fluid is shown in figure
2-6 [14].
Chapter 1.
11