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Slurry components in metal chemical mechanical planarization (CMP)

process: A review

Article  in  International Journal of Precision Engineering and Manufacturing · December 2016

DOI: 10.1007/s12541-016-0201-y

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 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12, pp. 1751-1762 DECEMBER 2016 / 1751
DOI: 10.1007/s12541-016-0201-y ISSN 2234-7593 (Print) / ISSN 2005-4602 (Online)

Slurry Components in Metal Chemical Mechanical

Planarization (CMP) Process: A Review

Dasol Lee1, Hyunseop Lee2, and Haedo Jeong1,#

1 School of Mechanical Engineering, Pusan National University, 2, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, South Korea
2 Department of Mechanical Engineering, Tongmyong University, 428, Sinseon-ro, Nam-gu, Busan, 48520, South Korea
# Corresponding Author / E-mail: hdjeong@pusan.ac.kr, TEL: +82-51-510-3210, FAX: +82-51-518-8442

KEYWORDS: Chelating agent, Chemical mechanical polishing (CMP), CMP mechanism, Metal, Oxidizer, Slurry

Chemical mechanical planarization (CMP) is a wet polishing technique employed to smooth the surface of various materials using
a combination of chemical and mechanical forces to achieve finer and longer lines on semiconductor devices. Among the published
papers related to CMP, the CMP metal slurry has been the primary focus, and it appears to be the main driver to improve the CMP
performance and quality for next-generation devices. Slurry can affect the removal rate, uniformity, defects, and selectivity between
the metal and the barrier layer. The material-removal mechanism of metal CMP is determined by the chemical reaction due to
chemical solutions compared to the mechanical action, which is due to the abrasiveness of the slurry. We verify that for each user,
a chemical knowledge of slurry is required to obtain preferred results. The basic chemical factors of metal CMP slurry are oxidizers,
chelating agents, and corrosion inhibitors. This review focuses on the role and effectiveness of each chemical solution by considering
the electrochemical characteristics. It will assist in determining the most appropriate solution to further the development of new slurry
for next-generation metal CMP.

Manuscript received: October 10, 2016 / Revised: November 15, 2016 / Accepted: November 16, 2016 (Invited Paper)

1. Introduction
NOMENCLATURE
Chemical mechanical polishing or planarization (CMP) is a
MRR = material removal rate manufacturing process that involves widely removing or planarizing a
Rc = chemical dissolution reaction rate variety of materials including metal, dielectrics, polymers, and other
Rm = mechanical abrasion rate thin-films associated with semiconductor fabrication. The global 1-5

A = wafer area surface planarity of a layer is critical for building the next layer for
kc = rate constant of the dissolution reaction three-dimensional (3D) integration technology, which aims to reduce
Ncm = number of surface sites available for the chemical dissolution device size. 6-8

or mechanical abrasion The semiconductor fabrication of wafers may be classified as the

Np = number of effective abrasive particles front end of line (FEOL) and back end of line (BEOL). The FEOL is
ΔG = Gibbs free energy change used to produce devices such as transistors within silicon, and the BEOL
n = number of electrons transferred per ion is the second part in which interconnects are formed on the wafer as the
F = Faraday constant metallization layer. 9

0
E = cell potential under standard conditions Metals are used as the conductor between individual electronic
γox = activity coefficients of oxidation metals components for transporting electrons in the device. The metals
γre = activity coefficients of reduction metals incorporated into the IC fabrication of the semiconductor device are
R corr = corrosion rate tantalum (Ta)/ titanium (Ti)/ cobalt (Co), tungsten (W), and copper
10-12
Icorr = corrosion current density (Cu).
Ecorr = corrosion potential W is used to fill the via and hole on the dielectric in order to connect
the interlayer metal line and the plug to improve the step coverage and

© KSPE and Springer 2016

 1752 / DECEMBER 2016 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12

13,14
alleviate electromigration. Copper metallization enables the
development of faster and more reliable integrated circuits than other
materials, which is due to its higher electrical conductivity and superior
15,16
electromigration resistance. Generally, a Cu interconnect line is first
constructed and a barrier metal is covered on the Cu line. Currently, Co
is one of the attractive barrier metals because of its favorable adhesion
to Cu seed layers, as well as the fact that it ensures conductive lining
17
inside trenches with Cu voids. The W plug is formed as an interlayer
metal connection, and another upper Cu line is formed as a multi-level
interconnection.
It is difficult to understand the CMP phenomena due to interactions
between the wafer, slurry, and pad. That is, it uses a combination of Fig. 1 Number of published papers related to CMP from 1995 to 2015
18,19
chemical and mechanical forces. The chemical solutions and
abrasives are referred to as the slurry. Therefore, the slurry is the most
important factor although its formulation for CMP is a complex science,
20
which is due to the synergistic interplay of chemicals and abrasives.
In addition, the slurry consists of a highly basic or acidic solution,
which results in pH changes in natural water and to toxic wildlife.
Further, it is a short lifespan consumable unlike the long life span
consumables such as pads, retaining rings, backing films, and
21-23
conditioner. Thus, the use of slurry is an important aspect of
reducing consumption through the ideal slurry that can increase the
24-26
material removal rate (MRR) and uniformity and defect free.
According to a survey of published papers shown in Fig. 1, there
has been a gradual increase in the number of studies regarding metal Fig. 2 CMP schematic on wafer-slurry-pad contact region
CMP slurry. This trend indicates that the studies into metal CMP still
belongs to uncharted territory. In view of the large volume of published
papers, we limit the scope of this review to the slurry chemical of the chemicals that are homogenously suspended in water. The chemically
metal CMP. Metal CMP slurry also consists of chemical solutions and reacted layer formed by chemical reaction between the wafer and slurry
abrasive particles. However, the chemical reaction at the wafer surface is removed with the mechanical abrasion caused by the sliding of
29
plays a more dominant role compared to the mechanical action caused abrasives and asperities of the pad. In the case of the metal CMP, the
by abrasives in metal CMP, whereas in oxide CMP, it is known that the general removal mechanism is the repetition of a generating passivation
30
film materials are mainly removed owing to mechanical abrasion by and its removal by mechanical abrasion. The passivation layer is a
27
slurry particles. chemically reacted layer, such as stabilized oxide on the surface, to
Therefore, this review paper focuses on the role of metal CMP protect the final surface from corrosion. Thus, the necessity and
slurry component and electrochemical characteristics in the underlying mechanism of metal CMP are generally proposed in terms of the
mechanisms involved in slurry design. Thus, this review provides a chemicals used in the slurry.
fundamental basis for the metal CMP process. In Section 2, we
introduce the material-removal mechanisms of metal CMP in terms of 2.1 Selectivity of metal CMP
chemical science. In Sections 3 and 4, we summarize the chemical Multilevel interconnection layers ae used with Cu and W. The
component of slurry and method used to design slurry by considering barrier materials, such as Ti/TiN, Ta/TaN, and Co, which are deposited
electrochemical behavior. between the wiring metal and dielectric, have a strong affinity for
oxygen. Ti/TiN is usually used to improve the adhesion of W to the
dielectric owing to the poor adhesive properties of W on SiO . Within
2

2. General Material-Removal Mechanism of Metal CMP
Material removal in the CMP process is a result of the complex
28
interaction between chemical and mechanical forces. Material removal
occurs when the rotating wafer surface is pushed against the soft polymer
pad attached on the rotating platen in the flooded slurry. The wafer is
mounted upside down on a backing film in a rotating carrier, and a
diamond conditioner is used to dress the pad to maintain its surface
roughness during polishing.
Fig. 2 shows the schematic of a wafer-abrasive (slurry)-pad contact
during the CMP process. The CMP slurry consists of abrasives and
the Cu module, the barrier metal is required to prevent the diffusion of
31,32
Cu into surrounding materials.
The metal CMP process is known as a damascene process, and was
introduced by IBM in 1997; damascene process means technique of
inlaying metal as the metal-deposition processes by CVD over patterned
33
trenches in dielectric. Therefore, the removal of the overburden is
carried out via metal CMP for 3D integration because the deposition of
metal is generally not perfectly uniform, as shown in Fig. 3. The
passivation layer of the upper area is removed by the mechanical
abrasion of the polishing pad and the abrasives, resulting in a new
surface becoming exposed to the slurry. However, the lower area is not
 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12 DECEMBER 2016 / 1753

30
Fig. 4 Material removal mechanism proposed by Kaufman for the
metal CMP process model

Fig. 3 Schematics of chip cross-sectional view and planarization steps

in direct contact with the pad, and is protected by the passivation layer
34
from etching. Because of this repetitive action, the upper area has a
larger MRR than the lower area. This is topographic selectivity caused
by selective mechanical contact, and achieves planarization.
The metal CMP has to finish at the oxide layer after removing the
barrier layer. Thus, the most important task in metal CMP is to minimize
the polishing selectivity between the interconnection material, barrier
material, and dielectric layers such as SiO . Chemical selectivity is the
2

ratio of the removal rate between two polished materials, and it affects
35
CMP defects such as erosion and dishing. The differences in the
properties of the wiring metal and barrier metal lead to variations in
removal rates, and this results in selectivity problems during CMP. Thus,
36
Wang et al. reported that a barrier-removal step is required after the
removal of Cu. Cu is polished very well by slurry, whereas the removal
rate of Ta is low as it is an inactive metal, which is difficult to etch.
Moreover, Fig. 3 shows a galvanic corrosion in which one metal is
preferentially corroded over another metal, and this results from the
electric contact of electrochemically different materials in the presence
of slurry (electrolyte). Galvanic corrosion occurs at the interface between
the barrier metal and Cu or W, and this is caused by the open circuit
potential (OCP). To reduce the galvanic corrosion of the Cu/Ru/TiN
37
films during CMP in the BEOL, Sagi et al. proposed a KMnO -based
38
4
slurry in the alkaline region. In addition, Kondo et al. reported that
galvanic corrosion can be prevented by selecting appropriate barrier
metals.
The selectivity and corrosion are mainly controlled by the chemical
solution of slurry. The metal removal caused by the designed slurries
can be achieved with an acceptable level of dishing or erosion toward
a single-step CMP with the best selectivity performance given an
understanding of the slurry chemicals.
2.2 Chemical science of material-removal mechanism
An early removal mechanism model was developed by Preston et
39
al., who proposed a removal rate that is caused by the pressure and
relative speed applied between the wafer and pad. The Preston model
considers only mechanical terms. However, the metal CMP process can
be explained using the chemical corrosion mechanism. Therefore,
30
Kaufman et al. introduced a more recent model that considers the
chemical effects of metal CMP as a simple qualitative route, particularly
for a W CMP. According to the mechanism proposed by Kaufman and
Fig. 5 Chemical reactions guided material removal depending on slurry
composition
shown in Fig. 4, chemical corrosion is a repetitive process that involves
the formation of a soft oxidation layer and removing it mechanically.
34
Paul et al. improved on the mechanism models using simple kinetic
expressions with a quantitative description of chemical reactions for the
MRR. The main idea of Paul’s model is that the complicated chemical
reactions and mechanical abrasion processes are separable. Paul’s
model can be expressed as:
MRR = (Rc + Rm )/A,
(1)
Rc = kc Ncm , Rm = kc ( Np /A ) Ncm
where Rc is the chemical dissolution reaction rate, Rm is the mechanical
abrasion rate, and A is the wafer area. kc is the rate constant of the
dissolution reaction, Ncm and Np are the number of surface sites available
for the chemical dissolution or mechanical abrasion and of effective
abrasive particles, respectively. Paul’s model can be used to explain the
MRR as a function of oxidizers by considering each chemical reaction
in more detail.
Generally, the chemical reaction of metal is divided into four cases
depending on the slurry composition, as shown in Fig. 5. M, Ox, C, and
I are the metal, oxidizer, chelating agent, and corrosion inhibitor,
respectively.
The soluble oxide state is not good, and leads to a primarily wet
etch. This results in isotropic removal with no topographic selectivity.
However, if the oxide layer is insoluble, it blocks further oxidation.
This is called a passivation layer, and has a high surface topographic
selectivity because abrasives in slurry mechanically abrade the oxide
 1754 / DECEMBER 2016 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12
layer. It is not possible to achieve an adequate layer using only the
oxidizer in Fig. 5(a). Therefore, some types of chelating agent binding
with metal ions were added to the slurry to compensate for the
40
inadequate layer in Fig. 5(b). As shown in Figs. 5(c) and 5(d), they
influence the decrease in dishing and scratch. The presence of a
corrosion inhibitor prevents chemical attacks of vulnerable areas of
41
anticorrosive polished surfaces, especially patterned wafer. Kondo et
42
al. proposed an abrasive-free polishing (AFP) using a chemical solution
without abrasives for the reduction of surface defects during CMP. The
abrasive-free slurry modifies the oxide layer by strengthening the
chemical reactions of the slurry. This is realized by adding additives
such as accelerators and suppressors to the CMP solution. Furthermore,
several chemical parameters also affect CMP results such as the type
43
and concentration of additives, as well as the pH of the slurry.
3. Analysis of Slurry Chemical
3.1 Role of slurry components
During CMP, slurry is spread over the pad. The function of the
slurry is to continuously deliver the chemical components and abrasive
particles to the entire wafer and to provide a means of removing
reaction layers of the protrusion on the wafer surface.
Different materials have different properties and characteristics, and
44
the CMP processes for each material require different slurries. It is
therefore important to understand the properties of slurry in order to
predict its behavior during polishing.
The abrasive component of slurry is delivered in solution phases
and abrades in a solid phase to provide the mechanical part of the CMP.
Most metals are thermodynamically unstable because of exposure to
ambient environment, and they have the tendency to be oxidized. Thus,
the chemical solution parameter of slurry is important in metal CMP,
whereas the abrasiveness of slurry is vital in dielectric CMP because of
45 24,32 46
its hydration mechanism. SiO 2and Al O abrasives are most
2 3
commonly used in metal CMP because of their high hardness and
47
stability. The basic chemical factors of metal CMP slurry are:
(a) Oxidizer: oxidize to metal ion
(b) Chelating agent: form a metal complex from oxidized metal
(c) Corrosion inhibitor: provide metal corrosion protection
(d) Surfactant: change the properties of the wafer surface
(e) pH adjustor: control the pH of the slurry
The oxidizer is a chemical species that removes an electron from a
metal surface. The anions of the carboxylic acid react with metal ions
to form insoluble or soluble salts as a passivation layer. In addition, the
chelating agent forms complexes with metal ions. A combination of the
oxidizer and chelating agent would help to obtain a better passivation
layer and high dissolution rate of the metal. The corrosion inhibitor
protects the surface of the metal from the oxidizer in order to minimize
dishing and erosion defects. There is a need for metal slurry because
the excessive chemical etching and oxidation deteriorate the surface
48
roughness of wafers.
A surfactant is a compound that changes the interfacial properties
by lowering the surface tension between a liquid and a solid for post
49
CMP cleaning. Surfactants have a hydrophilic polyethylene oxide
50 51
group and a hydrocarbon hydrophobic group. Dylla-Spears et al.
reported that a small amount of surfactants in polishing slurries can
52
prevent agglomeration. Li et al. showed that surfactant containing
slurry can reduce the coefficient of friction (COF). At low pressures and
velocities, the MRR was independent of the surfactant content, while at
high pressures and velocities, surfactant-containing slurries caused an
increase in the MRR.
Finally, electrochemical equilibria depend largely on the pH condition
of the slurry. The pH adjustor controls the acidity (i.e., less than pH 7)
or basicity (i.e., greater than pH 7). KOH, NH OH, and TMAH were
4
used as the pH adjuster to increase the pH of the slurry, while HCl
47,53 54
decreased the pH. Kang et al. reported that the pH of slurry affected
the etch rate, passivation, corrosion, and the removal mechanism. In the
solution, the metal exists in various states such as metal, metal ions,
and metal hydroxide. Each of these components performs a significant
role during the CMP process.
3.2 Electrochemical tool
The thickness of the passivation layer is around 1-3 nm thick, and
forms on the surface of the material to create a shell against corrosion.
The passivation layer is more brittle than metal film, and is removed
using abrasives. It can be produced only at a certain potential and specific
53
ranges of pH in a given slurry (electrolyte) solution. There are several
reports on thermodynamic method that can predict the corrosion
potential of the metal. The standard Gibbs energies is a thermodynamic
potential that is used to calculate the minimum work when a system
55
reaches chemical equilibrium at constant pressure and temperature.
The thermodynamic foundation of this approach follows the Nernst
equation, which relates the chemical component to the electrical
potential:
0 o
ΔG = –nFE = ΔG + RT ln K (2)
0 RT γ ox
E′ = E + ------- ln -----
- (3)
nF γ re
where ΔG is the Gibbs free energy change at any moment, ΔG is the 0
Gibbs free energy change under standard conditions of 1 atm pressure
and 298 K, n is the number of electrons transferred per ion, and F is
the Faraday constant (9.65 × 10 C). R is the gas constant (8.317 J/mol
4
K), T is the absolute temperature, and K is the equilibrium constant. E’
is the cell potential under specific conditions, E is the cell potential
0
under standard conditions, and γox and γre are the activity coefficients of
the oxidation and reduction metals, respectively. It is proposed that the
electrochemical reaction depends on E and the electrolyte, temperature.
0 56
For metal CMP, different electrochemical techniques have been used to
study the reaction tendency and corrosion reactions of metal.
Electrochemical measurements are used commonly via a three-
electrode system (reference, counter, and working electrode). The current
flows between the counter and the working electrode, and is controlled
by the voltage to maintain the potential difference between the working
57
and reference electrodes.
The potentiodynamic polarization technique is generally used to
produce a qualitative reaction, where the potential of the electrode is
varied at a selected rate by applying a current through the slurry for
 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12 DECEMBER 2016 / 1755

Fig. 6 The schematic illustration of potentiodynamic polarization curves Fig. 7 Typical corrosion plot showing anodic and cathodic components
of Cu-H O-glycine at different pH
2 of current using the Tafel extrapolation analysis

58
corrosion testing. Fig. 6 is a general polarization plot that shows the
59
theoretical potentiodynamic behavior.
59
Tripathi et al. investigated the Cu passivation kinetics using
potentiodynamic polarization curves. There is active corrosion at all
anodic potentials with a pH of 4, whereas for a pH of 11, there are
passivation zones at anodic potentials. The different pH values
demonstrate the different behaviors of metal illustrated in the curves.
The hydrogen evolution and oxygen reduction regions during cathodic
polarization are in the immunity domain in which the metal is not
undergoing oxidation. In anodic polarization, there are potentials in the
active, passive, and transpassive regions. The active region with the
oxidation reaction is in the dissolution domain, which means that the
metal is being oxidized. The decrease in the current is associated with Fig. 8 Pourbaix diagram (left) of Co-H O system and three-dimensional
2

ionic adsorption on the surface. When the active state changes to the
passive state, corrosion rate is reduced. In the passive state, the
corrosion rate of the metal is very slow. The passivation region
experiences little change in current as the potential is increased. In
addition, it tends to be destroyed because of its relative instability. The
transpassive region in which oxygen formation begins is broken down
60
into passivating films. Several published reports about the metal CMP
show that the curves are seen at potentials at which metal dissolves
actively as well as potentials at which metal is passivated.
Then, the equation can be expressed as a corrosion rate, R corr:
61
pH-potential diagram (right) of Co-design slurry system (Adapted from
Ref. 65 on the basis of OA)
The Pourbaix diagram is widely used to discuss corrosion issues
64
according to the relationship between the electric potential and the pH.
It is obtained by performing thermodynamic equilibrium calculations,
and was developed to enable the prediction of various metallic stable
64
forms. Aksu et al. showed that glycine significantly extended the
solubility range of Cu by comparing the Pourbaix diagram of the Cu-
H O-glycine system and the Cu-H O system.
2 2

Rcorr = Ia/nF (4) However, many researchers have observed that many chemicals in
the slurry have behavior that differ from what is expected using only
where n and F are the same as described in Eq. (3); I is the current the Pourbaix diagram of metal-H O-one of chemicals. Furthermore,
2

density, and a is the atomic weight. Icorr is proportional to the corrosion
rate.
To evaluate the corrosion rate from such polarization measurements,
we measured the current density using the scanning electrode potential
(Tafel plot), as shown in Fig. 7.
The Tafel extrapolation analysis is effective in that it helps us to
obtain detailed information of the oxidation-reduction reaction shown
62 63
by the metal and slurry in the CMP. Zheng et al. reported that the
corrosion rates could be calculated from the intersection of the cathodic
line and anodic line at the Tafel extrapolation used for metal CMP.
They showed that the Tafel plot changed according to the pH.
from the diagram, it is difficult to obtain the relative corrosion rate, as
well as calculations in the case where the slurry contains many chemical
species.
65
Thus, Ichige et al. proposed a 3D pH-potential diagram that includes
the current density. Fig. 8 shows that the changes in the passivation area
depend on the combination of the metal and chemical solution. The two-
dimensional conventional Pourbaix diagram expresses various stabilities
of oxidized and reduced species between the metal and limited chemical
species only. On the other hand, the 3D pH-potential diagram was found
to be a powerful method to analyze the corrosion issue between metal
and the slurry design slurry for an actual CMP process because it
 1756 / DECEMBER 2016 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12

experimentally obtained a result of the potential-current density diagram Table 1 A classified table of oxidizers for metal CMP
in all pH regions. Oxidizer Cell potential 71
Example
Another method is surface analysis. X-ray photoelectron spectroscopy Peroxide group E 2 2 2 0
H O /H O 72 24,47
Na O , H O
2 2 2 2

(XPS) analysis provides detailed information on the bonding (-O-O-) =1.766 V

0 - - 73 74 75

characteristics and elements of surfaces such as Cu O on the Cu wafer.

2
66 Halogen E 3 IO /I NaClO , H IO , HBrO ,
3 5 6 4

76
(F, Cl, Br, I) =1.085 V KIO
Each element produces a characteristic set of XPS peaks at characteristic 0 - -
3

E 3 2 NO /NO 73 77 78,79
binding energy values. XPS can be explained considering the effect of Nitrate ion HNO , Cu(NO ) , Fe(NO )
3 3 2 3 3
=1.085 V
oxidation in surface (top 0-10 nm) by irradiating a solid surface with Chromate/Sulfate/ E 0 2+
4 MnO /Mn 74 80 37
67 68
a beam of X-rays. Deshpande et al. studied the role of CMP slurry K Cr O , Na SO , KMnO
2 2 7 2 4 4
Manganate =1.491 V
additives using XPS and SIMS (secondary ion mass spectroscopy).
SIMS is used to analyze the composition of solid surfaces by using
secondary ions to sputter a primary ion beam to reveal the elemental
composition of the surface. This was carried out to understand the
interaction of additives and any changes in the metal surface chemistry.
XPS analysis is used to authenticate the results obtained using SIMS.
However, it cannot be directly applied to CMP because the chemical
state of the surface may be altered during the sample preparation. Thus,
a combined method involving both thermodynamic prediction from the
Pourbaix diagram and XPS analysis would be the best approach to
predicting the chemical state of the surface that is formed during CMP.
Consequently, the electrochemical reactions of metals, such as
dissolution, oxidation, and corrosion, are key parameters in slurry
design for metal CMP. The MRR of metal CMP is determined by the
generation rate and quality of the passivation layer.
Fig. 9 Potentiostatic polarization behavior of a metal in a solution
containing H O at different concentrations: (a) no H O (b) 1% H O
2 2 2 2 2 2

4. Chemical Components in Metal CMP Slurry (c) 3-5% H O (d) 7-10% H O

2 2 2 2

Many kinetic factors control the relative rates of the surface-film

6
formation and its removal. It is important to find the right balance
between an appropriate removal rate and the uniformity of the surface.
Slurries for the metal CMP typically contain chemicals that assist in
forming a passivating layer on the wafer surface. In this section, we
evaluated various chemicals as chemical components in metal slurry
based on the variation in electrochemical change, which depends on the
addition of chemicals.
4.1 Oxidizers
Many researchers have studied the influence of oxidizers on the
CMP removal rate, static etch rate, and surface contamination. For
electronegativity that draws bonding electrons to themselves. A nitric
oxide compound, chromium compound, sulfate compound, and
manganese compound are fairly strong oxidizing agents. Usually,
between five and seven electrons are added to these atoms, reducing it
to the highest oxidation state +5 (N) +6 (Cr, S) +7 (Mn) because these
compounds have many electro-negative oxygen atoms that can easily
82
remove electrons from metal. These compounds affect the improvement
83 84 85
of the MRR of hard materials such as SiC, GaN, and sapphire. The
positive ion can be either H or different alkali elements such as Ca, Na,
and K.
Of the oxidizers, ferric nitrate Fe(NO ) was used as the first oxidizer 3 3

78 79
metal slurries, it is common to use oxidizers to increase the removal during the early stage. Lim et al. and Seo et al. proposed Fe(NO ) , 3 3

rate. Oxidizers remove electron or donor oxygen from other atoms. KIO and H O individually or in combination as oxidants for W CMP.
3 2 2

They generate metal ions from metal to increase the oxidation state of However, Fe(NO ) causes excessive oxidation and results in
3 3

69,70 3+
the wafer via an oxidation-reduction (redox) reaction with metal. contamination by Fe ion-formed tungsten oxidation of FeCuO or 2

For example: FeWO . 4

Oxidation reaction: M → M + 2e 2+ -
Hydrogen peroxide (H O ) is a widely used oxidizer in CMP slurry
2 2

Reduction reaction: Oxidizer (ex. H O ) + 2e− → 2OH−

2 2 because it is the simplest and most stable peroxide, and a powerful
Precipitation formation: M + 2OH− → M(OH)
2+
2 oxidizing agent without contaminated wafers. Du et al. showed the 86

M(OH) is a passivation layer. Table 1 shows the most frequently

2 effect of H O on the oxidation of Cu in CMP slurry. Electrochemistry
2 2

used oxidizer, which is the oxygen atom transfer agent. Strong oxidizers
have more positive E . 0
The oxygen-oxygen chemical bond of peroxide is unstable and
was used as a tool to examine the role of oxidizers because the chemical
reactions of oxidizers were electron-transfer reactions.
Fig. 9 shows the effect of H O concentration on the electrochemical
2 2

easily split into reactive radicals via homolytic cleavage due to the
81
existence of only small quantities in nature. Compounds containing
halogen are highly reactive for removing electrons because of the high
86
behavior under static conditions at a certain pH. It suggests that control
of the quantities of oxidizer additives is crucial. The corrosion potential
increases with an increase in H O concentrations. Many researchers 2 2
 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12
explained that these results may be corroded because of the inhibited
cathodic reaction and the enhanced anodic reaction that form metal
ions. It is believed that the formation of a passive layer increases the
barrier to the transport of ionic and electronic currents.
However, the maximum corrosion current density appears at a
87
concentration of about 1% H O . Hernandez et al. reported the removal
2 2
rate with H O concentration in Cu CMP slurry using XPS. Their
2 2
results show that the concentration of H O determines the thickness of
2 2
the passivation film as Cu O. The passivation film becomes thicker and
2
denser at higher concentrations of H O . The thick oxidation layer acts
2 2
as a boundary layer, preventing the diffusion of chemical reactants.
Oxidation depends on the diffusion of oxygen into the metal, and it thus
causes a decrease in the diffusion length. The thinning of the passivation
layer leads to higher ionic diffusion rates for repeating the formation
and removal of the layer, and therefore a higher removal rate. It is
preferred that the oxidizer be present in the slurry in an amount ranging
from about 0.5% to 5%.
88
In addition, Chathapuram et al. studied the CMP of Ti and TiN in
aqueous solutions with and without 5% H O using electrochemical
2 2
techniques. The removal rate of TiN is higher compared to Ti. In spite
of the slurry at the same concentration of H O , potentiodynamic 2 2
polarization has a different behavior when other additives are added to
the slurry or when the target material is different.
4.2 Chelating agents
Chelating agents are often referred to by several names, such as
complexing agent or binding agent. The passivation layer generated by
only an oxidizer has a weak ionization balance and generates metal
ions. Chelating agents promote the production of new metal ions to
catalyze oxidation and the degrading of emulsions by reducing metal
89
ions. Liu et al. investigated the effect of the synergic ratios of the
chelating agent oxidizer in terms of the dishing value and MRR of Cu.
It can be well passivated when the oxidizer is three times the value of
the chelating agent in the slurry.
Their anions form passivation films as metal-chelating agent
complexes by reacting with metal ions. The metal complex is a chemical
species that has a metal atom in a central position to which various
90
ligand species are bonded as coordinate covalent bonds.
Ligands are ions or molecules that bond to a central metal atom or
ion, and which have unshared pairs of electrons such as O, N, and S
donor atoms. The coordinate covalent bond is formed when both
electrons forming the bonding pair of electrons are provided by the
same atom. Ligands act as Lewis bases (electron pair donors), and the
central atom acts as a Lewis acid (electron pair acceptor) to form a
91
covalent bond.
Acids containing carboxyl (-C(=O)OH; succinic acid, acetic acid,
oxalic acid) or amine groups (-NH ; ethylene-diamine) or amino acids
2 rate and prevent defects during CMP. They are adsorbed on the metallic
(-COOH and -NH ; amino butyric acid, glycine) or hydroxyl (-OH;
2 surface, in the process blocking the active corrosion sites.
citric acid) are widely used as complexing agents for metal slurry as
well as for post CMP cleaning solutions. For instance, glycine reacts
with metal ions and then forms a metal-glycine complex, as shown in
Fig. 10.
62
Jang et al. showed a different chelating effect with three chelating
agents of different groups, respectively, using polishing experiments.
According to their research, glycine is the optimum agent type among
DECEMBER 2016 / 1757
Fig. 10 Formation of metal-glycine complex by chemical reaction with
glycine as a chelating agent and metal ions
92
ethylene-diamine and citric acid on Cu CMP. Gorantla et al. reported
the effects of three different amino acids, namely glycine, serine, and
cysteine in the Cu slurry containing H O . Their results indicated that
2 2
the concentration of generated -OH radical alone may not be responsible
for the enhancement of Cu MRR, but other parameters such as the pH
and metal-complex interaction may also be involved. In addition, Patri
93
et al. reported that the MRR of Cu decreased with an increase in the
distance between the -NH and -COOH in an amino acid at all pH values
2
94
except for a pH of 4. Seal et al. reported the surface modification of
Cu along with the glycine concentration by electrochemical analysis
and XPS. I is increased and E is decreased as the complexing agent
corr corr
95
concentration is increased. Li et al. investigated the effects of chelating
agents on reducing the galvanic corrosion between Co and Cu in alkaline
slurry. These results implied that chelating agents could inhibit the
corrosion of Co with a higher erosion potential than Cu by increasing
the pH of the slurries with -OH.
In short, chelating agents:
(a) must contain at least a lone pair of electrons
(b) tend to have higher chelating effects of multiple bonded ligands
than a single ligand
(c) has a stability state on a pentagon or hexagon ring
(d) can be ordered by their hardness such that hard metal ions
prefer weak field ligands
Chelating agents with monodentate ligands are usually less stable
than those with polydentate (multiple bonded) ligands. They form a very
strong metal complex with five or six chelate rings. In addition, certain
metal ions have a preference for certain ligands. In general, soft metal
ions prefer strong field ligands, whereas hard metal ions prefer weak
field ligands.
4.3 Corrosion inhibitor
Corrosion inhibitors in metal CMP have been used to protect the
surfaces of metals from oxidization in order to control the dissolution
41
The chemical nature, i.e., organic or inorganic, which is categorized
according to whether or not they contain carbon, can be either synthetic
or natural chemicals. Most inhibitors are organic compounds that contain
at least one benzene ring attached directly to a nitrogen atom. The
presence of nitrogen assists adsorption by a lone pair, as the lone pair
can be donated to the metal surface according to classical Lewis acid/
base theory. Corrosion by only nitrogen is intended to be limited. It is
 1758 / DECEMBER 2016
Fig. 11 Chemical structure and proposed structure of the polymeric
[Metal-inhibitor] of (a) Benzotriazole (b) 1, 2, 4-triazloe
known that a benzene ring is an excellent donor of electrons. The
greater the electron density around the nitrogen, the stronger is the bond
that is formed between the nitrogen and metal. The layer caused by this
bond is essential to prevent the corrosion of the metal itself, and provides
a barrier to the dissolution of metal in the slurry.
Typical compounds can function as inhibitors, such as benzhydryl
compounds and azole. C-N-C bond angles perform best of all at
corrosion inhibition. Benzhydryl compounds contain two benzene rings
adjoining a single carbon atom. Azoles are a class of five-membered
heterocyclic compounds containing at least one other non-carbon atom
96
(N, S, O) as a part of the ring.
Generally, amines with higher electron densities on their nitrogen
atoms bind more strongly to metal surfaces, and they are more effective
inhibitors. Because amines are considered as hard bases, they adsorb
efficiently to metal surfaces, which are considered as hard acids. A hard
base reacts more easily with a hard acid than with a soft one.
The presence of an adsorbed metal-inhibitor layer on the metal
surface creates a zone of high ohmic resistance between the metal surface
and the electrolyte. This resistance slows down or stops galvanic
reactions and the loss of electrons from the metal surface.
Well-known inhibitors are benzotriazole (BTA) and 1, 2, 4-triazloe
96
(TAZ), as depicted in Fig. 11.
Over the past two decades, many researchers have extensively studied
the effect of BTA on metal corrosion. Many reports indicate that the
metal residue and dishing are a trade-off in slurry formation because
the addition of the inhibitor into CMP slurry reduces the removal rate.
97
Chen et al. clarified that the localized thickness variation is resolved
98
by a lower concentration of the inhibitor in Cu slurry. Brusic et al.
reported that the resulting BTA-Cu film was not removed effectively,
and that high levels of organic residues could form on the Cu surface,
reducing yields.
76
Jiang et al. reported a synergetic effect between BTA and the non-
ionic surfactant in slurries so as to yield a desirable MRR by the
99
formation of an incomplete Cu-BTA thin film. Besides, Jiang et al.
considered TAZ as a promising alternative to the conventional BTA.
The surface planarity of Cu was improved by the addition of TAZ
although there was a little compromise in the removal rate.
Organic inhibitors have both cathodic and anodic actions to protect
using a film adsorption. Fig. 12 shows a theoretical potentiostatic
INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12
Fig. 12 Potentiostatic polarization diagram: electrochemical behavior
of a metal in slurry (a) versus without inhibitor (b) with organic
inhibitor
100
polarization curve of a slurry with and without inhibitor. After the
addition of the inhibitor, the corrosion potential remains the same, but
the current density decreases from Icorr to I'corr. It can be seen that the
addition of the inhibitor reduces the metal corrosion rate.
5. Future Study
Many attempts have been made to realize an ideal metal CMP slurry
by varying the chemical parameters of slurry such as the types of additive,
the concentration of additives, and the pH of slurry. Ahead of the
understanding of fundamental principles of the chemical components,
the slurry can be designed to provide effective polishing to metal layers
at a desired removal rate and uniformity, while minimizing surface
defects. This depends on the choice of the oxidizing agent, chelating
agent, corrosion inhibitor, and other useful additives.
However, it is sensitive to the chemical environment associated with
CMP. The global environmental issue requires the use of greener
technology in order to reduce slurry consumption. In addition, there is
the post-CMP cleaning, which is accompanied by the CMP process, and
the removal of the particle and chemical contamination caused by the
slurry. This process wastes a large amount of chemicals and water, and
has a negative effect on CMP. Thus, corrosion inhibitor-free slurry and
abrasive-free slurry are currently being developed as CMP slurry for a
post-CMP cleaning step to enable the easy removal of organic-Cu
residues on wafers.
It has been proposed that the development of next-generation
slurries is required to overcome CMP challenges. The slurry remains a
challenging issue with respect to the need for new materials, complex
integration schemes, the need to be defect-free, and cleaning
requirements.
To verify the reliability of the device yield of products, it is important
to understand fundamental slurry chemicals and new chemical analysis
such as 3D pH-potential diagram, and this can be done using new
strategies, as well as the development of new chemistry studies.
 INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING Vol. 17, No. 12
ACKNOWLEDGEMENT
This work was partially supported by the National Research
Foundation of Korea (NRF) grant funded by the Korea government
(MSIP) (No, 2016R1A2B4011466), and was partially supported by
Basic Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education
(NRF-2015R1D1A1A01059266).
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