www.semiconductor.

net
September 2008
the semiconductor industrys
technical authority
TM
evelopments in IC manufacturing
are increasing the demand for in situ
concentration measurement as liquid
chemicals are consumed in significantly
greater quantities for chemical mechani-
cal planarization (CMP), photolithography, electrochemi-
cal deposition (ECD) and surface preparation. At the 65
nm node and beyond, process windows are narrowing to
the point that increasingly smaller variations in chemical
concentration adversely affect wafer defect levels and, most
importantly, yield. In addition, there is increasing pressure
to minimize the environmental impact by reducing liquid
chemical waste streams.
1
The impact: overall cost of owner-
ship (CoO) is on the rise.
A solution to rising CoO is process control of liquid
chemicals with highly accurate concentration and analy-
sis systems that take measurements continuously, in real
time and at point-of-use, where chemicals are blended or
delivered. In addition to increased yields, real-time sensors
contain costs by reducing chemical consumption, waste
streams and wafer scrap while increasing efficiencies and
productivity.
1
Existing technologies for measuring concentration in-
clude conductivity, near-infrared (NIR) absorption spec-
troscopy, ultrasound, titration and index of refraction (IoR).
However, proven effective in other industries, the unique
demands of liquid concentration sensors for IC manufac-
turing may make a particular technology less appropriate,
whether caused by in situ location, real-time response, reso-
lution or size.
This article discusses existing technologies, as related
to semiconductor applications, and presents case studies
comparing IoR technology to auto-titration and other sen-
sor technologies.
Sensor technologies
Based on a fundamental laboratory technique, titration
remains the gold standard for sensor accuracy and resolu-
tion. This method collects a sample from the process line,
combines it with reagents, and analyzes the concentration.
A titration unit may be linked to the process line (auto-titra-
tion) or operate as an unconnected unit (manual titration).
If connected to the process line, it may be called inline, but
fluid only travels in one direction, toward the unit, where it
is processed, analyzed and then disposed of, creating a waste
stream. It is not inline in the sense that process fluid flows
through it on the way to its destination in real time.
In spite of its large size and slow speed, where one read-
ing may take 45 minutes, titration is widely employed in
semiconductor manufacturing today. Even if readings are
only intermittently taken, titration remains the point of
reference. In processes such as CMP and wafer cleaning,
batches of chemicals are circulated, spiked and disposed of
in accord with the experience of the technical staff, which is
informed by a history of titration measurements.
Titration, however, is impractical for measuring the
concentration of more than one liquid chemical at a time.
The ongoing expense of chemical reagents and replacement
parts, such as O-rings and probes, leads to high CoO.
Conductivity
Conductivity works by measuring voltage across cylindrical
probes placed in a liquid chemical. This method provides
reliable measurement at a low cost across a narrow dynamic
range of concentration measurements, beyond which reso-
lution deteriorates. A single unit is typically calibrated for a
particular dynamic range. If measurements are required in
Concentration
Sensors
Curb Rising CoO
Ron
Chiarello,
Jetalon Solutions Inc.,
Pleasant Hill, Calif.,
www.jetalon.com
Noritsugu
Ishida,
Swagelok Co.,
Solon, Ohio,
www.swagelok.com
In situ, real-time
concentration
monitoring will
be vital to the
industrys move
to 65 nm CDs
and below
to address
the need for
increased yield
and reduced
waste.
1. The CR-288 concentration monitor sensor and its internal
configuration shows the layout of the light source, sapphire
window and photodiode array in relation to the liquid.
Concentration Monitor
Light
source
Photodiode
array
Sapphire
Liquid
1-25186480 eprint.indd 1 10/29/08 3:51:24 PM
an additional range, a second sensor is calibrated. Common
applications in semiconductor manufacturing, in fact, often
exceed a single units dynamic range.
A second limitation is that only chemicals containing
ions can be measured, which excludes the measurement of
solvents, such as benzene, methanol, acetone and hydrogen
peroxide. Finally, the probe must make contact with the
fluid stream, which may affect flow or raise the prospect of
contamination.
NIR absorption spectroscopy
For NIR absorption spectroscopy, a fiber optic probe (light
pipe) is placed in the fluid stream and carries a light signal
back to a box for analysis. Unique to this technology is its
ability to read and identify the individual fingerprints of
several chemicals inside a single blend. NIR spectroscopy
also measures concentration, but with limited resolution
or accuracy. Therefore, it is most often used in cases where
identifying the chemicals in the mix is more important than
tracking concentration.
Measurements are slow, produced at a rate of about one
every 30 seconds and, in a fab environment, the long fiberop-
tic cable may present challenges in terms of its stability.
Furthermore, NIR spectroscopy units
are comparatively expensive, have a large
footprint, and the sensors may present
challenges in terms of calibration.
A similar form of this technology, ul-
traviolet (UV) visible spectroscopy, mea-
sures UV wavelengths instead of infrared.
Its benefits and limitations are otherwise
similar to those of NIR spectroscopy.
Ultrasound
Ultrasound is based on measuring the
speed of sound through a fluid. Because the speed of sound
is dependent on a liquids pressure, temperature and flow
rate, these variables must be controlled or compensated for.
With the addition of a pressure regulator and flow control-
ler, variables may be controlled and ultrasound can provide
a high degree of resolution and accuracy in concentration
measurements. Bubbles in the liquid will affect the accuracy
of the reading, but this problem may be addressed through
digital signal processing techniques.
Index of refraction
Index of refraction (IoR), a well-established technology
only recently used by chipmakers, works by shining a light
beam on a liquid chemical and then measuring the IoR. If
the mixture or concentration changes, so will the IoR.
Refractive index values are determined in two ways:
transmission geometry and optical reflective geometry.
In transmission geometry, light must travel through the
liquid before it can be measured, while in optical reflec-
tive geometry, a light source is directed toward a sapphire
crystal on the liquid and the light reflecting off the surface
is measured.
Transmission geometry is affected by the opaqueness
and other properties of the fluid. The light beam can be
absorbed or diffracted, both of which can produce incorrect
measurements. Absorption increases as the liquid becomes
more opaque, and diffraction occurs when the light is
knocked off course by particles or bubbles. To lessen the ef-
fects of absorption and diffraction, transmission geometry
uses a narrow fluid path, typically a maximum of 0.5 in.,
which can present challenges in terms of flow.
In contrast, optical reflective geometry is not affected
by the opaqueness of the fluid because the measurement
is taken at the optical window-liquid interface. In the
Swagelok CR-288 concentration monitor, for example,
light from an LED is directed at the surface of a sapphire
window in contact with the fluid (Fig. 1). It strikes the
sapphire at multiple points and angles (
s
) and is either
absorbed by the liquid or reflected and scattered upward
into a photodiode array. For reflectance angles (
S
) smaller
than the critical angle (
C
), light is mostly reflected off of
the window. For angles greater than
C
, light is both re-
Analyzers used
Comparison of Concentration Measurements
H
2
O
2

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
w
t

H
2
O
2
)
3.3
3.25
3.2
3.15
3.1
3.05
3
2.95
2.9
2.85
CR-288 results (%wt H
2
O
2
) TR2 Titrator results (%wt H
2
O
2
) All pairs
Tukey-Kramer
0.05
2. An analysis of
variation using the
Tukey-Kramer test with
the SAS-JMP software
shows the sample-to-
sample variation for the
concentration monitor is
comparable with that of
the auto-titrator.
3. In an application aimed at
measuring the change in water
concentration, the graph indicates that
index of refraction (IoR) technology
produces results with higher resolution
than a near-infrared (NIR) absorption
spectrometer.
1
6
:
3
8
1
9
:
1
2
2
1
:
4
6
0
:
1
9
2
:
5
4
5
:
2
8
8
:
0
2
1
0
:
3
6
1
3
:
0
9
1
5
:
4
3
1
8
:
1
7
2
0
:
5
1
2
3
:
2
6
1
:
5
9
4
:
3
3
7
:
0
7
9
:
4
1
1
2
:
1
5
1
4
:
4
8
1
7
:
2
2
1
9
:
5
7
2
2
:
3
1
1
:
0
5
IoR vs. NIR
%

o
f

H
2
O
2

c
o
n
s
u
m
e
d
Time
43
42.5
42
41.5
41
40.5
40
39.5
39
NIR
CR-288 IoR
Concentration Sensors Curb Rising CoO
SEMICONDUCTOR INTERNATIONAL September 2008 EQUIPMENT COMPONENTS AND SUBSYSTEMS www.semiconductor.net 2
1-25186480 eprint.indd 2 10/29/08 3:51:25 PM
flected off of the window and transmitted through it. By measuring
the change in scattered light intensity as a function of
s
,
C
can be
determined. From Snells law,
C
is related to the liquids IoR. Snells
law (n
1
sin
1
= n
2
sin
2
) is the relationship between angles of incidence
and refraction for a wave impinging on a surface between two media of
different IoRs.
Because the IoR will change as temperature changes, the output is
passed through an additional algorithm.
Software enables fine adjustments in resolution where concentra-
tion is plotted against time for extended data logging. Average time per
reading may be adjusted from one reading every second to one every 10
seconds or one every minute, and so on. For example, one data point
per 10-second interval means that each data point represents an average
taken over 10 readings (one per second). Similarly, the Y-scale may be
altered so that the user may zoom in on a transition of interest.
The CR-288 concentration monitor can measure four different
chemicals at the same time over a refractive index (RI) range of 1.25-
1.45, with resolution of better than 5
10
-6
. Response time is <1.2 sec. The fol-
lowing case studies test IoR technology
against an auto-titrator and other tech-
nologies in third-party simulations of
semiconductor industry applications.
Case study #1: real-time
monitoring for CMP
In a joint study conducted by Chartered
Se mi c onduc t or Ma nuf a c t ur i ng
(Singapore) and Kinetics Process Systems
(Singapore), the CR-288 concentration
monitor was installed in the Kinetics
slurry blending system to monitor hy-
drogen peroxide concentrations in the
slurry batch. An auto-titrator was also
employed, and the two sets of results
were compared.
2
The blending and distribution system
is composed of two blending stations that
work together to provide a continuous
supply of slurry to multiple polishers. The slurry is blended and tested
in one system before it is available for distribution in the global loop,
which services the polishers.
For the study, the concentration monitor was retrofitted to one of the
blending systems containing copper CMP Slurry E. The auto-titrator
remained in place, measuring the same slurry mixture as the concentra-
tion monitor. An ANOVA using the Tukey-Kramer test with SAS-JMP
software showed that the concentration monitors performance was
comparable with the auto-titrators. In fact, the concentration monitors
sample-to-sample variation was better and the time required to prepare
the slurry through circulation in the loop was reduced (Fig. 2).
The concentration monitors digital display unit (DDU) made
concentration trends and data available in the control room, which
eliminated the need for an offline computer. With elimination of the
auto-titrator, the concentration monitor enables an appreciable reduc-
tion in the slurry systems CoO.
Case study #2: comparing
NIR, conductivity, IoR
In a back-end-of-line (BEOL, post-etch clean-
ing) application, a mixture of solvent (ST250)
and water is employed. As a normal part of
the process, the water evaporates or is other-
wise consumed.
The objective of the study, which was
conducted by a third party, was to monitor
water loss and replenish the water at a given
concentration. The concentration monitor
and a NIR spectrometer were employed in the
process tool to measure water concentration.
Figure 3 demonstrates that the resolution of
the concentration monitor is higher than the
NIR spectrometer.
In a separate but similar study, also con-
ducted by a third party, the application used
a mixture of solvent (EKC-265) and water.
The concentration monitor was compared
to a conductivity measurement instrument.
Measurements were taken in the process tool.
While the concentration monitor accurately
EKC-265
IoR vs. Conductivity
I
o
R

@

2
0

C
Concentration of added H
2
O
C
o
n
d
u
c
t
i
v
i
t
y

(
m
S
/
c
m
)
Conductivity
1.458
1.456
1.454
1.452
1.450
1.448
1.446
1.444
1.442
4.00
3.80
3.60
3.40
3.20
3.00
2.80
0% 2% 4% 6% 8% 10% 12% 14% 16% 18%
Temp at this data point was 64C while the rest were ~67C
IoR @ 20C
4. IoR technology plots a decrease in water concentration, but a conductivity-based measurement tool
is unable to accurately measure the same change over the better part of the range.
Concentration Sensors Curb Rising CoO
Out of
range 7
IoR Measurements of Photoresists
I
o
R

@

2
0

C
T
e
m
p
e
r
a
t
u
r
e

(

C
)
Samples
22
20
18
16
14
12
10
8
1.45000
1.44500
1.44000
1.43500
1.43000
1.42500
1.42000
1.41500
1.41000
1.40500
1.40000
1.39500
1.39000
1.38500
1.38000
1.37500
1.37000
1.36500
1.36000
L H M F G C J B I A E K D
Samples
10
Air-dry spikes
post-acetone
1.361
acetone flush
IoR @ 20C
Temperature
5. IoR technology was able to clearly distinguish 11 out of 15 photoresists tested. The initial nine
detected are shown. Temperature has been corrected for 20C.
www.semiconductor.net EQUIPMENT COMPONENTS AND SUBSYSTEMS September 2008 SEMICONDUCTOR INTERNATIONAL 3
1-25186480 eprint.indd 3 10/29/08 3:51:25 PM
References
1. R. Chiarello et al., Using a Real-Time, Point-
of-Use Sensor to Control Liquid-Chemical
Concentration, Micro Magazine, May 2005.
2. C. Aparece, C. Wacinski and S. Rajan, CMP
Slurry Blending Process Optimization and
Cost Improvements Using Real-time Concen-
tration Monitoring, Adv. Semi. Manufact. Conf.,
June 2007.
3. R. Jee, S. Pepper and D. Stedman, Positive
Identification of Lithographic Photoresists Us-
ing Real-Time Index of Refraction Monitoring
for Reduced Cost of Ownership, in press.
Posted from Semiconductor International, September 2008. Copyright Reed Business Information, a division of Reed Elsevier, Inc. All rights reserved.
Page layout as originally published in Semiconductor International has been modified.
#1-25186480 Managed by The YGS Group, 717.399.1900. For more information visit www.theYGSgroup.com/reprints.
plots the decrease in water, the conductivity
tool is unable to accurately measure the change
in concentration over the better part of the
range (Fig. 4).
Case study #3:
differentiating among
photoresists
In a study simulating a photoresist feed line, as
one used for delivery to a lithography tool, the
objective was to determine whether RI tech-
nology could be used to differentiate among
all possible photoresists. The study was con-
ducted by Swagelok at a third-party labora-
tory setting, Micron Technology Inc. (Boise,
Idaho).
3
The larger question in forming the study
was whether the concentration monitor could
be used to mistake-proof the lithography pro-
cess by indicating in real time if and when the
wrong photoresist was fed into the system, a
mistake that could cost hundreds of thousands
of dollars in scrapped wafers.
Two experiments are summarized here. In
the first experiment, the goal was to determine
if the CR-288 concentration monitor could
draw clear distinctions among 15 different
photoresists, including 10 deep ultraviolet
(DUV) photoresists. The 15 samples were
randomly fed into the concentration monitor
and, for comparison, into a benchtop refracto-
mer, Leica model AR600. In between samples,
the two devices were cleaned. Each sample was
fed into the two devices three times.
Initial results showed that the concentra-
tion monitor was able to produce distinct
peaks for nine out of the 15 photoresists (Fig.
5). Two additional photoresists (samples G
and K) became identifiable once the range
and calibration of the sensor was adjusted.
The four photoresists not detected (samples L,
M, N and O) have RIs >1.46, which is out of
range for the concentration monitor.
For eight of the 10 DUV photoresists,
the margin of error between the concentra-
tion monitor and benchtop device was <0.5%.
Variance for repeatability between the three
measurements taken of the 11 photoresists
that the concentration monitor could detect
was very good at 2.75 10
-4
RI.
The second experiment was designed to
simulate an application where a continuous
stream of different photoresists would be
delivered to a lithography tool without the
possibility of cleaning or purging in between.
Different samples were injected continuously,
sequentially and randomly into the same con-
centration monitor. Figure 6 shows that for
nine out of 10 DUV photoresists, 20 mL of
fluid was enough to generate a clearly identifi-
able step change. When the Y-scale was ad-
justed, a step change between the two DUV
photoresists with the closest RIs (samples D
and E) was also identifiable.
The study concludes that the concentra-
tion monitor is able to draw clear distinc-
tions between 10 out of 10 DUV pho-
toresists and, therefore, would be able to
identify an incorrect photoresist flowing into
a lithography tool, trigger an alarm, and
enable a system to divert flow away from
the tool to waste, avoiding scrap or rework.
Conclusion
Sensors for semiconductor manufacturing are
effectively meeting the new demand for min-
iature, accurate, real-time, inline measurement
of chemical concentrations. In particular, IoR
technology is proving effective in making fine
determinations in applications concerning
wafer cleaning, etching, lithography, ECD
and CMP. These developments set the stage
for significant reductions in environmentally
sensitive waste, lost product and CoO for con-
centration sensors. SI
Concentration Sensors Curb Rising CoO
6. As indicated, in 9 out of 10 deep ultraviolet (DUV) resists tested, 20 mL of fluid was enough for IoR
technology to generate an identifiable step change. With Y-scale adjustment, the step change between
the DUV photoresists with the closest refractive indices (samples D and E) could also be detected.
IoR Measurements of DUV Resists
I
o
R

@

2
0

C
IoR @ 20C
Temperature
1.44500
1.44000
1.43500
1.43000
1.42500
1.42000
1.41500
1.41000
1.40500
Time
T
e
m
p
e
r
a
t
u
r
e

(

C
)
22
20
18
16
14
12
10
Sample G
No purging
between
samples
Sample H
Sample B
Sample J
Sample F
Sample I
Sample
D
Sample
D
Sample
E
Sample
E
Sample K
2 syringes
Ronald Chiarello is president and CTO of Jetalon Solutions, with 20 years of experience in high-
tech R&D at Stanford University and the University of Chicago (Hyde Park, Ill.). A NATO fellow, he
has won the Department of Energy Award for Excellence in Research and the University of Chicago
Pace Setter Award for Outstanding Contributions in Synchrotron X-ray Techniques. He received a
B.S. in physics from the University of California-Santa Barbara and an M.S. and Ph.D. in physics from
Northeastern University in Boston.
Noritsugu Ishida has been with the Swagelok organization since 1982. He is presently a senior
field engineer at Swagelok Japan Inc. (Nishinomiya), providing engineering support for Swagelok
products. He holds a B.N.E. from Tokai University, and is a voting member of Gas & Facility
Committee and Liquid Chemical Committee of SEMI Japan.
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