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Characterisation of Oxide-CMP Slurries with Fumed-Silica Abrasive Particles

Modified by Wet-Jet Milling

Conference Paper · January 2004

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 Characterisation of Oxide-CMP Slurries with Fumed-Silica Abrasive Particles
Modified by Wet-Jet Milling

Gerfried Zwickera, Harald Jacobsena, Wolfgang Lortzb, Eric Stachowiaka, Ralph Brandesc

a
Fraunhofer Institut für Siliziumtechnologie, Itzehoe, Germany
b
Degussa AG, Hanau, Germany
c
Degussa Corporation, Piscataway, N.J., USA

Abstract

Different dispersions of fumed-silica particles have been treated in a high energy wet-jet mill in
order to modify the morphology of the particles from the more flake-like shape of the fumed-
silica agglomerates to the spherical shape of colloidal-silica particles. The polishing behaviour of
wet-jet milled samples has been compared with untreated and colloidal-silica samples. It has
been observed that the removal rates, the dependency of the removal as a function of the
product of platen speed and down force and the obtained surface roughness do not change
substantially. However, the post-CMP cleaning behaviour indicates changes in the morphology
of the particles. This is supported by high shear-rate viscosity measurements which clearly
show the modification of the dispersions by high energy wet-jet milling. Some implications of
high shear rates on the CMP process are discussed at the end of the paper.

Introduction

Planarisation by means of CMP is an enabling technology for the manufacturing of ULSI

devices. In future, the structure size on wafers is further decreasing with increasing integration
density. Accordingly, the size of the abrasive particles used in the CMP slurries have to be
adapted appropriately.

Colloidal-silica based slurries consist of isolated, small spherical particles and tend to give
smooth, scratch-free surfaces during CMP. The drawback of colloidal-silica based slurries is the
reduced removal rate in comparison to fumed-silica based slurries.

The primary particles in fumed-silica based slurries produced by flame hydrolysis of SiCl4, H2
and O2 are joined and form larger agglomerates or aggregates. As it is difficult to estimate the
size of the agglomerates, the characteristics of different products are described by their BET
surface area. The size of the primary particles of the investigated AEROSIL® dispersions varies
between 5 and 40 nm which corresponds with BET surfaces between 300 and 50 m2/g. Due to
the rough surface morphology of the particles, fumed-silica based slurries typically show higher
removal rates. It can be predicted that modified, more spherical agglomerates of fumed-silica
particles will be needed to fulfil future CMP needs.
Slurry Mixing

The production process of colloidal silica from liquid reactants automatically leads to stable
dispersions of amorphous silicon dioxide particles in water with adjustable average particle
sizes of 5 – 200 nm1. The main fabrication step for the production of fumed-silica slurries is the
dispersion of dry silica powder in water by employing shear forces. The stability of the
dispersion is controlled by the pH of the solution.

Different milling processes with milling energies (dispersion forces) between 102 and 1011 J/m3
can be employed to disperse the abrasive particles in the solution. Table 1 compares the
different milling processes and their inherent energy densities. Dissolvers, stirrers or rotor/stator
engines yield relatively low shear forces with mixing times of minutes to hours and leave the
particles unchanged. On the high end of the scale, in wet-jet mills very high shear forces lead to
a strong interaction of the particles. Fig. 1 shows the principle of the wet-jet mill (WJM). The pre-
dispersed slurry can be compressed up to 2500 bar. The divided flows 1 and 2 expand through
diamond nozzles 3 and 4. The high-velocity slurry jets collide and interact in the mixing chamber
5 and perform a partial grinding of the particles. The very high milling energy of the wet-jet mill
alters the morphology of the agglomerated primary particles with the expected result of smaller,
more spherical, but also differently agglomerated particles.

Method Principle Volume-specific Dispersion Applications

Energy Density Time
J/m3 sec
Dissolver 102 - 104 101 – 104 General Applications
Stirrer

Rotor/Stator 103 - 106 10-3 - 103 Pharmaceutical, Coating,

and Cosmetic Applications

Agitator Ball 105 - 108 10-4 - 101 Paint Industry

Mill

Planetary 106 - 109 10-4 - 102 Food and Chemical

Kneader/Mixer Industry

High Pressure 106 - 1010 10-6 – 10-1 Food, Pharmaceutical and

Homogeniser Chemical Industry

Wet-Jet Mill 107 - 1011 10-8 – 10-3 Production of nano-

Particles

Table 1: Comparison of different milling processes for the dispersion of small particles
Fig. 1: Operation principle of the wet-jet mill

Experimental

Aim of the presented work was the modification of fumed-silica particles in polishing slurries by
using milling and dispersion technologies in order to obtain particles which behave more similar
to colloidal-silica particles. The basic idea is the purposive transformation of the irregularly
shaped fumed-silica particles to agglomerates with spherical shape by using high milling
energies. For this purpose dispersions have been prepared by either using a conventional
rotor/stator mill or the novel high-energy wet-jet mill. In all cases the pH-value of the dispersions
has been adjusted with KOH to pH = 10.5, the fumed-silica concentration for the polishing tests
is 12.5% by weight.

Beside several dispersions of Degussa AEROSIL® fumed-silica powders with varying BET
surface areas between 50 and 300 m2/g, also a commercially available fumed-silica based ILD
slurry has been treated with the high energy wet-jet mill. The CMP polishing behaviour of the
dispersions have been characterised and are compared with fumed-silica and colloidal-silica
products used in semiconductor manufacturing.

All polishing experiments have been performed under production-near conditions by using a
Peter Wolters PM200 Gemini CMP cluster tool. DF200 backing films and IC1400 k-grooved
pads, both from Rodel Inc. have been employed for polishing. Removal rate results are
obtained from 49-point measurements. The 200 mm wafers were coated with 1000 nm CVD-
TEOS oxide. After CMP the wafers have been brush cleaned with water.

Results

In Fig. 2 the removal rates RR of different slurries are plotted as a function of the product of
platen speed and down force p*v. The straight line of a strict Prestonian behaviour

RR = k p v

could only be observed with the colloidal-silica slurry of Fig. 2a. The fumed-silica based product
of Fig. 2b shows a sub-linear increase of RR with p*v. A further analysis of the data showed that
the process can be best described by the equation

RR = M p5/6 v1/2
first proposed by Tseng and Wang2. This fits well with the general observation that colloidal-
silica slurries have a linear dependence while fumed-silica slurries typically show a kind of
square-root behaviour.

The graph of Fig. 2c shows the dependence of the fumed-silica product treated 2x in the wet-jet
mill with 2500 bar. The mean removal rate of the modified commercial ILD fumed-silica slurry is
about 7 % lower than the untreated commercial ILD slurry, while the sub-linear behaviour does
not change. From these results it can be concluded that wet-jet milling does not change the
morphology of fumed-silica slurry particles substantially. In particular, fumed-silica particles
have not been transformed into colloidal-like abrasive particles by the high energy treatment.

Fig. 2 a-c: Removal rate as a function of the product of platen speed and down force for colloidal
(left), fumed (middle) and fumed, modified by wet-jet milling (right) slurries

Nevertheless it could be shown that repeated treatment with different pressures in the wet-jet
mill changes the polishing behaviour of fumed-silica dispersions. In Fig. 3a the mean RR of a
test slurry with Degussa AEROSIL®90 particles, dispersed by using a rotor/stator mill, is
compared with AEROSIL®90 dispersions additionally modified in the wet-jet mill with different
treatment cycles. While a mild treatment with 2x 750 bar leads to a slight increase in RR, the
values decrease with more cycles or higher working pressures up to 5x 2500 bar. It seems that
a moderate wet-jet milling first activates the abrasive particles while more pronounced
treatments might change the shape of the particles with the effect of reduced oxide removal.

Fig. 3a (left): Removal rates of AEROSIL®90, dispersed with a rotor/stator mill and differently treated in
the wet-jet mill
® 2
Fig. 3b (right) Removal rates of AEROSIL dispersions with BET surfaces between 50 and 300 m /g.
®
AEROSIL OX 50 consists of molten, spherical silica particles and can be regarded as
"colloidal-like". All dispersions are wet-jet milled with 2x 2500 bar
A comparison of the removal rates of 2x 2500 bar WJM-treated dispersions of AEROSIL®
particles with BET surface areas between 50 and 300 m2/g is given in Fig. 3b. The graph shows
decreasing removal rates for increasing specific surface areas, slightly increasing again for
AEROSIL®300. For comparison, the RR of AEROSIL® OX 50, due to a higher flame
temperature during synthesis a product consisting primarily of spherical primary particles with a
broad size distribution, is added. Due to the spherical shape of the particles the dispersion
behaves more like a colloidal-silica slurry with the typical reduced removal rate.

It can be concluded from these results that the different AEROSIL® products have a much
higher influence on RR than the treatment of particles in the wet-jet mill.

Fig. 4a (left) Relative numbers of light point defects (particles 0.2 – 1.0 µm) after brush cleaning with
®
water for AEROSIL 90, dispersed with a rotor/stator mill and differently treated in the wet-
jet mill
Fig. 4b (right) Relative numbers of light point defects (particles 0.2 – 1.0 µm) after brush cleaning with
® 2
water for AEROSIL dispersions with BET surfaces between 50 and 300 m /g treated in
the WJM with 2x 2500 bar

A comparison of the light point defects (LPDs) as a measure for particles after brush cleaning
with water is given in Figs. 4a and b. The measurement has been performed on a Censor
ANS 100 surface particle counter, the relative numbers of LPDs corresponding to 0.2 – 1.0 µm
particle size are plotted for different or differently treated AEROSIL® dispersions.

From Fig. 4a can be taken that the number of particles after post-CMP cleaning increases with
the energy of the wet-jet milling. This leads to the conclusion that wet-jet milling is breaking the
abrasive particles into agglomerates which are sticking more strongly on the surface. This could
be due to the formation of smaller particles or more irregularly shaped particles with more
contact points.

Fig. 4b shows the particles after post-CMP cleaning for 2x 2500 bar wet-jet milled AEROSIL®
dispersions with different BET surfaces. Dispersions from powders with smaller primary
particles (larger BET surfaces) leave more particles behind after post-CMP cleaning than larger
primary particles. These results allow the conclusion that wet-jet milling is modifying the
dispersions more pronounced than the relatively minor changes in removal rates would suggest.
Fig. 5 Roughness of oxide surfaces after polishing with different slurries

An effect of wet-jet milling on the post-polish surface quality cannot be observed. Fig. 5
compares the colloidal-silica product with some different or differently treated fumed-silica
slurries. It can be observed that both the fumed-silica slurry and the AEROSIL® dispersions with
or without WJM treatment have a twice as high post-polish roughness Ra than the colloidal
product. All roughness data have been obtained by using an AFM. The result underlines the
finding that wet-jet milling of fumed-silica dispersions has no substantial influence on material
removal. The polishing properties of the colloidal-silica slurry could not be achieved despite the
high energy treatment. It needs to be kept in mind that the evaluated AEROSIL® dispersions
were all produced on a laboratory scale and differences to commercial ILD fumed-silica slurries
may be possible.

Nevertheless WJM alters the particles in the dispersions. Beside the cleaning results this fact
can also be deduced from viscosity measurements for high shear rates. All viscosity data shown
have been obtained from using a high pressure capillary viscometer3. The particle concentration
of the fumed-silica slurry and all AEROSIL® dispersions was 25% except the colloidal-silica
slurry, which has a 30% particle content.

From the Figures 6a-c and previous publications3 it can be taken that the viscosity of the slurries
or dispersions remains constant for lower shear rates and starts to increase above 200,000 to
800,000 s-1. Fig. 6a shows the data for the fumed-silica slurry and the AEROSIL®90 dispersion
with and without wet-jet mill treatment. For comparison, the viscosity of the colloidal-silica slurry
is added. The untreated fumed-silica slurry and the AEROSIL®90 dispersion show nearly
identical viscosity developments. The same behaviour can be observed for both samples
treated in the WJM (2x 2500 bar). Interestingly, the curves look quite similar to the colloidal-
silica sample, but shifted to higher shear rates. Both fumed-silica dispersions have been altered
to more colloidal-like slurries with respect to the high shear-rate viscosity.

A treatment of AEROSIL®90 dispersions with different milling energies leads to a principally

unchanged behaviour for low energy (2x 750 bar), but shows a higher peak viscosity. The result
changes to the colloidal-like curve for higher energies (2x 1500 bar, 2x 2500 bar), as depicted in
Fig. 6b. This corresponds with the finding, that the removal rate of mildly treated dispersions
increases slightly, while for higher energies the RR decreases again. The milling results for
2x 2500 bar of various AEROSIL® particles are shown in Fig. 6c. While AEROSIL®130 is also
shifted to a colloidal-like slurry, the AEROSIL®200 dispersion is comparable to the AE90 sample
at 2x750 bar. This indicates that for dispersions with large BET surfaces even higher milling
energies are necessary to obtain colloidal-like viscosity behaviour.
Viscosity [mPas] Viscosity [mPas]

35 35

30 30 AE90 2x750 bar

25 25

20 AE90 R/S 20 AE90 R/S

Fumed
Fumed
15 15

Colloidal Colloidal
10 10
AE90 2x1500 bar
5 Fumed WJM 5

AE90 WJM AE90 2x2500 bar

0 0

100,000 400,000 700,000 1,000,000 1,300,000 100,000 400,000 700,000 1,000,000 1,300,000
Shear rate [1/s] Shear rate [1/s]

Viscosity [mPas]

35

AE200 2x2500 bar

30

25

20
Fumed
15

Colloidal
10
AE90 2x2500
5
AE130 2x2500 bar
0

100,000 400,000 700,000 1,000,000 1,300,000

Shear rate [1/s]

Fig. 6a (top left) Viscosity for shear rates between 100,000 and 1,500,000 s-1 of the fumed-silica slurry
®
and the AEROSIL 90 dispersion with and without WJM treatment. The viscosity of the
colloidal silica is shown for comparison
®
Fig. 6b (top right) Viscosity of differently wet-jet milled AEROSIL 90 dispersions
®
Fig. 6c (bottom) Viscosity of AEROSIL 90, 130 and 200 dispersions after wet-jet milling 2x 2500 bar

In conclusion it seems that wet-jet milling is altering the morphology of the aggregated particles
of fumed-silica slurries, but is not leading to the desired spherical shape of colloidal-silica
slurries with smoother post-polish surfaces. It can be speculated that the milling energy is too
high and is not only "grinding" the outer protrusions of the flake-like particles, but is smashing
the agglomerates with the consequence that the smaller particles form new agglomerates.

Discussion

All polishing experiments have been performed on blanket oxide layers. The influence of the
modified fumed-silica slurries on structures, i.e. the planarisation behaviour of the samples has
not been investigated. As the WJM treatment has a pronounced influence on the measured
viscosity for high shear rates it can be speculated that the treatment also changes the CMP
results on planarisation. Depending on the platen speed and the distance between polishing
 pad and structure (i.e. the thickness of the slurry film), shear rates up to 106s-1 or even more can
occur during CMP for local slurry film thicknesses of 1 µm and a relative wafer-to-platen speed
of 1 m/s. As the viscosity is one of the main factors for the coefficient of friction and the realised
removal rate, a local increase of viscosity for high shear rates at the "up-features" will influence
planarisation. With a high pressure slit capillary viscometer with a slit gap of 50 µm, which
achieves shear rates up to 4,000,000 s-1, viscosities of up to 50 mPa s have been measured for
a colloidal-silica slurry3.

Therefore appropriate polishing experiments on structured wafers have to be performed, which

lead to high viscosity effects due to the local high shear rates appearing at protruding pattern
features. Additionally it has to be considered that high shear rates at these patterns modify
fumed-silica slurry particles comparable to the high shear forces in the WJM. Therewith a
change of the behaviour of the slurry during the CMP process due to the slurry residence time
under the wafer has to be taken into account.

References
1
K. Vogt, "Kieselsole fuer CMP", Proc. 4th CMP Users Meeting, Munich, 2000
2
W.-T. Tseng and Y.-L. Wang, "Re-examination of Pressure and Speed Dependences of
Removal Rate during CMP processes", J. Electrochem. Soc., Vol.144, No.2, p.L15, 1995
3
W. Lortz, F. Menzel, R. Brandes, F.Klaessig, T. Knothe and T. Shibasaki, "News from the M in
CMP – Viscosity of CMP Slurries, a Constant?", MRS Symp., San Francisco, 2003

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