PERFORMANCE CHARACTERIZATION OF SMALL ABRASIVE COLLOIDAL

SILICA CMP SLURRIES

Rakesh K. Singh and Christopher R. Wargo Bill Mullee Benno Milmore
Entegris, Inc. Silco Electronic Materials ON Semiconductor

Summary and Conclusions

Chemical mechanical planarization (CMP) processes for the next generation IC devices require increasingly stringent
management of consumables such as slurries, slurry filters, CMP pads, pad conditioners, retaining rings, and post-
CMP clean brushes, for minimum CMP CoO and minimal defectivity. This paper reviews key considerations for CMP
slurry characterization, metrology, handling, and filtration. Efficient slurry management should consider slurry abrasive
type/composition, oxidizer/chemical additives, large particle counts (LPC), mean particle size distribution (PSD), pH,
conductivity, weight % of solids, viscosity, filter LPC retention, pressure drop, flow-rate, filter lifetime, slurry
usage/turnover rate, cumulative turnovers before consumption, and the slurry blending and distribution system “the
pump” behavior. Slurry characterization studies help in identification of sensitive parameters to mix slurry accurately
and monitor its health during storage, usage, and replenishment.
This paper presents characteristics of smaller-particle, high-purity colloidal silica CMP slurries designed
specifically for ULK dielectric layers. Comparative performance of Silco EM-5530K and EM-7530K slurries is presented
in terms of wafer polishing rate, NU, and particle defectivity employing different CMP tools, pads, and competitive
slurries. These newly designed next generation slurries provide precise and consistent removal rates, minimal
defectivity, and maximum planarity across the wafer surface. Another objective of this study was to evaluate tighter
graded density depth filters (Entegris Planargard®) to identify optimum filtration scheme for above slurries in the
manufacturing and point-of-use (POU) applications. Planargard® CS0.5 and Planargard® CL0.3 (nominal ratings 0.5
and 0.3 micron, respectively) filters provide target reduction in cumulative LPC ≥ 0.56 micron. Present study
demonstrates the benefits of CMP consumables laboratory and limited scale fab evaluations to generate slurry
quality/health management information.

Slurry Management and Health Monitoring Parameters

Slurry management challenges include: tighter purity and blend accuracy requirements of new CMP slurries, non-
settling abrasive and extended post-blending useful life, minimal variability in slurry and blend chemical properties of
different lots (and over time of a lot during recommended storage periods), and the uncertainties of oxidizer/additives
decay/adjustments with time. Also, next generation processes demand significantly more stringent particle counts, size
distribution, and filtration specifications. Detection and removal of defect-causing large particles at small
concentrations and size in newer slurries is posing unique challenges. Many new slurries are not well defined and
require fine-tuning for specific processes. Further, there is enhanced emphasis on reducing CoO of CMP process and
consumables, and continued collaboration, consolidation, and introduction of new products.
Slurry health or quality monitoring parameters include: LPC (≥ 0.56 or 1.01 micron particles), mean PSD, zeta
potential, pH, ORP (oxidation reduction potential), conductivity, viscosity, refractive index, total dissolved solids (TDS),
weight % solids and density (or specific gravity), oxidizer and additives concentration and ionic contamination. In oxide
slurry blending and distribution, there is a greater emphasis on particle agglomeration and LPC control using filtration,
and wt % solids, LPC and PSD monitoring. Similarly, in tungsten, copper and STI slurries, the focus areas include
quick abrasive settling characteristics, oxidizer level monitoring and replenishment, and density, LPC and PSD
variation with time. The slurries are typically chemically buffered and there is insignificant pH variation with changes in
the blend ratio. Also, ORP does not change with mix ratio in most slurry blends.
Conductivity and TDS usually have good sensitivity to blend ratio, but cannot be used as an independent control
parameter, since conductivity values vary in different lots of the same slurry (not controlled by manufacturers), and also
vary with aging of the same slurry. Silica oxide slurry blends are controlled using density, whereas tungsten and copper
CMP slurry blends are controlled using an autotitrator or other ultrasonic, RI, or NIR based analyzers for
monitoring/replenishment of the oxidizer. Silica slurries are typically slow settling, whereas alumina- and ceria-based
slurries have quick settling behavior. Settling rate in formation can help in estimating the required minimum flow
velocity of slurry in global loop.
 Slurry Characterization and Filtration
Slurry bench-top and handling characterizations provide useful insights on slurry metrology and health management
challenges. Next generation CMP slurry metrology tools should be able to measure the chemical and/or oxidizer
concentration(s) as well as the LPC and PSD on a real-time basis, and use this information for the CMP process
control. Slurry Bench-top tests focus on: slurry components and blend properties, sensitivity analysis of blend
consistency measurement parameter, recommended mix ratio ± 20%, effect of DI water dilution, and abrasive settling
characteristics for incoming slurry - source drum or pail and sample bottles.
Slurry handling tests investigate abrasive settling behavior and redispersion effort needed for incoming slurry,
storage tank or daytank, global loop settling, loop shutdown effects and minimum flow rates for keeping abrasives in
suspension. Slurry lifetime testing during extensive handling typically focus on slurry properties monitored in
continuous recirculation tests at various time points (e.g. day 0, 1, 2, 3, 4, 7 and sometimes up to 28 days). These
extensive characterizations involve filter optimization tests, such as point-of-use (POU) and global distribution loop
filtration, and slurry delivery system cleaning protocol development.
The removal of large, defect-causing particles without changing the PSD spread or mean PSD of abrasives is
critical for the CMP slurry performance. LPC growth in slurries is typically managed using post-blending, global loop
and/or point-of-use (POU) filtration. Filtration can effectively remove large particles if the size of particles to be
removed, e.g., ≥ 0.5 μm or ≥ 1.0 μm, is (at least) one order of magnitude larger than the mean working particles (to be
retained) in the slurry. Tighter POU filters flow rate, pressure-drop and lifetime can be significantly affected due to
mean PSD and LPC changes in extensively handled slurries.
Using optimum rating filters in the global loop and at POU, and limiting total number of slurry turnovers before
consumption is helpful in obtaining stable CMP performance in such applications. Typical slurry manufacturing
processes target 90 % and higher reduction of cumulative LPC at ≥ 0.56 μm. Single-pass filtration solutions using
graded density, multiple thin-layer, pleated depth media filters, or membranes can provide required large particle
retention, depending on the slurry abrasive and chemical composition.

Characteristics of a New Colloidal Silica Slurry

• Unique pH-Stable
Colloidal Silica Slurries
• Consistent, Precise
PSD’s Lot-to-Lot
• Wide Variety Particle Sizes
• Very High Purity…< 10 PPM • Significantly Lower Defect
Na+ Counts
• Trace Metals, Chlorides <0.1 • Stable Low-pH Particles
PPM
• Excellent Product Stability
pH Stabilization Process

KOH
CMP
Low-pH Mix
Lev 1
Slurry Feed Tank
pump

Cleanroom
Filtering & Lev 2
Packaging pump

13
75nm High Purity Colloidal Slurry
12.5

12
Spec. Limits
11.5

11
pH
10.5

10
Silco Process
9.5
Industry Standard
9

8.5 DAYS
180
135

1 50

165
120
105
75
60

90
15

30

45
0
Effect of Trace Metals on ILD Polish Performance Silco 75nm ILD Slurry Performance
Normalized Defects Down Force Normalized Defects Polish Rate
Slurry [Al] [Ca] [Cr] [Fe] [Ni] [Na] Slurry (psi)
Uniformity
(A/min)
& Microscratches & Microscratches

198 198
Silco <1 <0.1 <0.1 <1 <0.1 <10 Silco 7.0 6.0% 3800
164 164
588-658
Standard <100 <1.8 NA <6.5 <10 <50
268-316 588-658
Standard 7.0 7.4% 3700
233-277 268-316
Supplier X NA NA NA NA NA NA
451-533
NA 233-277
Typical <50 <5 <1 <20 <100 <100 Alternative 7.6 5.5 to 8.0% 3650
451-533
- Experiments run by a volume IC Fab
- All metals are specs and units in ppm - Experiments run by a volume IC Fab
- All slurries are based on colloidal silica particles - All slurries are based on colloidal silica particles
- Comparable removal rate and uniformity - All slurries have same solids content of silica

ILD Polish Objectives:

Present study evaluates comparative performance of Silco EM-5530K and EM-7530K high purity colloidal silica slurries
in terms of polishing rate, NU and particle defectivity using different CMP pads and other similar slurry products. These
next generation slurries provide precise and consistent removal rates, minimal wafer defectivity, and maximum
planarity across the wafer surface.
• Compare defect performance of Silco EM products vs POR slurry and alternate slurry in qualification using blanket
furnace TEOS wafers.
• Perform 1000A HF etch to highlight and provide insight into microscratch performance.
• Compare blanket polish rates and non-uniformity using Silane based oxide film.
• Tests performed on Novellus Momentum and Applied Materials Mirra platforms.
Particle count post 1000Å HF Particle count post 1000Å HF
Particle count post polish Particle count post polish highlight for micro-scratches
highlight for micro-scratches

Slurry 1, Novellus w/ IC1000 Pads, Wafer #1 Silco EM-7530K, Novellus w/ IC1000 Pads, Wafer #1

EM-5530K and EM-7530K Wafer Polishing Rate, NU and

Particle Data Summary Pump
Platform Pad Slurry Rate NU Particles Depth
Novellus IC1000 EM-5530K 2496 3.8 2.67 Filter
Novellus IC1000 EM-7530K 2221 1.5 1.33
Novellus IC1000 Slurry 1 2364 6.8* 14.67 Pressure Pressure
Novellus IC1000 Slurry 2 2366 6.9* 0.67 Gauge, P1
Gauge, P2
AMAT IC1010 EM-5530K 3143 6.38 16
AMAT IC1010 EM-7530K 2862 6.57 2.67 Weight
AMAT IC1010 Slurry 1 2990 5.37* 19.67 Scale
AMAT IC1010 Slurry 2 3098 5.01* 12.3
AMAT PPG EM-5530K 3243 4.43 4 Slurry Supply
AMAT PPG EM-7530K 3066 4.66 4.67
Figure 1. Schematic of Filter Test Set-Up.
ILD Polish Observation:
• Defect performance of Silco EM-7530K is favorable compared to alternate colloidal slurries on both the Novellus
Momentum and Applied Materials Mirra platforms.
• Removal rate and non-uniformity are comparable on both Novellus and Applied platforms.
• Silco EM-5530K exhibited slightly higher removal rate relative to EM-7530K.

Filtration Characterization of Colloidal Silica Slurries

The main objective of this study was to evaluate Entegris Planargard® CS and Planargard® CL series CMP slurry high-
retention filters’ large particle retention performance with Silco Electronic Materials Concentrated Colloidal Silica
Dispersion (referred as “silica dispersion” now onwards in this document) and EM-5530HP Oxide CMP Slurry (referred
as “oxide slurry”) both with ~32 weight % solids.
This single-pass application filtration target was to reduce LPC ten fold for ≥ 0.56 micron abrasive particles for the
slurry dispersion (for bulk slurry filtration) and reduce LPC in the oxide slurry for POU application. Filtration with
Planargard® CS0.2 and CS0.5 (nominal ratings 0.2 and 0.5 micron, respectively), Planargard® CL0.3 and CL0.7
(nominal ratings 0.3 and 0.7 micron, respectively), and Planargard® CL1.0, CS1.0 and CMP1 (all nominal rating 1
micron) filters achieved the required reduction (90+ %) in the cumulative LPC ≥ 0.56 micron, for the silica dispersion.
1.5E+05 6.0E+06 5.0E+05
Cumulative # of Particles / mL

Cumulative # of Particles / mL
Cumulative # of Particles / mL

Silica Dispersion Silica Dispersion EM-5530HP

(# Part / mL > = Diameter)

(# Part / mL > = Diameter)

(# Part / mL > = Diameter)

CS0.2 Filtrate CL1.0 Filtrate CS0.2 Filtrate

CS0.5 Filtrate 5.0E+06 4.0E+05
CS1.0 Filtrate CS0.5 Filtrate
CL0.3 Filtrate
1.0E+05 CMP1 Filtrate CL0.3 Filtrate
CL0.7 Filtrate 4.0E+06
3.0E+05
3.0E+06
2.0E+05
5.0E+04 2.0E+06
1.0E+05
1.0E+06

0.0E+00 0.0E+00 0.0E+00

0.1 1 10 0.1 1 10 0.1 1 10
Particle Diameter (microns) Particle Diameter (microns) Particle Diameter (microns)

Figure 2. Colloidal Silica Dispersion source and Figure 3. Colloidal Silica Dispersion source and Figure 4. EM-5530HP oxide silica slurry source and
Planargard® high retention filters LPC distribution. Planargard® 1 micron filters LPC distribution. Planargard® high retention filters LPC distribution.

The filtration with the tightest CS filter (Planargard® CS0.2) showed retention of ~99 % for the dispersion and 91
% for the oxide slurry, whereas the slurry filtration with Planargard® CS0.5 and CL0.3 resulted in ~78 % and 89 %
reductions, respectively, in the cumulative LPC ≥ 0.56 micron. The slurry source and filtrate samples collected at
different time points were analyzed for LPC using a Particle Sizing System Accusizer™ 780 APS system (employing a
top injection dilution chamber with single stage auto dilution with measurements started before on-line dilution of the
injected samples). Slurry samples were also tested with Horiba LA-930 mean particle size distribution (PSD) analyzer.
This study demonstrates that Entegris Planargard® CS0.5 and CL0.3 filters can be employed to achieve the
required retention of the cumulative LPC ≥ 0.56 micron in a single pass bulk filtration of colloidal silica dispersion.
Since Planargard® CMP1 filter has much lower initial pressure drop, it may be used on upstream side of the
Planargard® CS0.5 filters to achieve relatively longer filter lifetime for CS0.5 filter.
Another alternative would be to employ Planargard® CL0.3 filter for tighter retention, and use CMP1 filter
upstream. Since the tested silica dispersion and the oxide slurry have relatively smaller mean particle size than
majority of oxide abrasive slurries, using CMP1 filter in the above configuration is expected to provide good life-time for
CMP1 as well as CS0.5 (or CL0.3) filters. Based on the present study, Planargard® CS0.5 or CL0.3 filters may be
employed for the POU filtration of silica slurry.

Acknowledgments
The authors would like to thank Dr. Peter Burke, Clint Jones, and Dr. Ashwani Rawat for their contributions to this
study and numerous insightful discussions. Sincere thanks are due to slurry manufacturers for providing CMP slurry
samples for the slurry characterization evaluations, Levitronix GmbH for providing a magnetically levitated centrifugal
pump for this study, and Contaminations Control Solutions Team at Entegris, Inc., for their support of this project.
Planargard, Mykrolis, and Entegris are registered trademarks of Entegris, Inc., Levitronix is a registered trademark of Levitronix
GmbH, AccuSizer is a trademark of Particle Sizing Systems.