NSF/SRC Engineering Research Center for

Environmentally Benign Semiconductor Manufacturing

Peterson, et al. 1 DI Water Reduction in Rinse Processes
Contributions
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Manufacturing Peterson, et al. 1 DI Water Reduction in Rinse Processes Contributions by:
Thomas W. Peterson, University of Arizona Andy Hebda, University of Arizona Thomas
Roche, Motorola Corp. Eric Hansen, Santa Clara Plastics  1999 Arizona Board of Regents
for The University of Arizona

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Manufacturing Peterson, et al. 2 Overview DI water use during rinsing: –~ 10 3 gallons/wafer
==> ~10 7 - 10 8 gallons/year (SEMATECH) Minimal recycle and reuse across the industry
Primary objective: CLEAN WAFERS

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Manufacturing Peterson, et al. 3 Indicators of “Clean Wafers” ON-LINE –Resistivity in the
Rinse Tank OFF-LINE –Particle Counts on Wafer Surface –Elemental Analysis of Wafer
Surface –Device Characteristics Testing

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Manufacturing Peterson, et al. 4 Terminology Resistivity –Primary measurement of ionic
concentration of rinse water. The higher the ion concentration, the lower the resistivity. –[=]
MW - cm Conductivity –The inverse of resistivity. For dilute solutions, conductivity is
proportional to ionic concentration –[=] 1/ (MW - cm)

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Manufacturing Peterson, et al. 5 Terminology (cont’d) Integrated Conductivity –The
conductivity in the rinse water integrated over the time period required to “recover” from the
chemical burden introduced to the system by the wafers Carryover –Amount (moles or grams)
of chemical “carried over” with the wafers and the boat from »chemistry tank to first rinse
tank »first rinse tank to second rinse tank

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Manufacturing Peterson, et al. 6 “Typical” DI Water Resistivity (M  - cm) Clean water,
high flow conditions (greater than 11 gpm): 17 - 18+ Clean water, low flow conditions: 8-17
or lower Rinse bath containing wafers, immediately following chemistry: <<0.01 (mdl for
monitor)

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Manufacturing Peterson, et al. 7 Resistivity, Conductivity and Ionic Concentration

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Manufacturing Peterson, et al. 8 Integrated Conductivity and “Carryover”

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Manufacturing Peterson, et al. 9 Resistivity is the Primary Measurement
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Manufacturing Peterson, et al. 10 K(t) = 1/ R(t)

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Manufacturing Peterson, et al. 11 Resistivity and Conductivity

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Manufacturing Peterson, et al. 12 Integrated Conductivity

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Manufacturing Peterson, et al. 13 Continuous Stirred Tank Model

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Manufacturing Peterson, et al. 14 CSTR Characteristics

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Manufacturing Peterson, et al. 15 Evidence of CSTR

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Manufacturing Peterson, et al. 16 Evidence of CSTR (cont’d)

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Manufacturing Peterson, et al. 17 CSTR vs. PFR Model For a theoretically pulsed input, the
response of a PFR reactor is significantly smaller than that of a CSTR reactor. Input
Response 0 PFR CSTR

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Manufacturing Peterson, et al. 18 Hypothesis: Wafers can be adequately “cleaned and rinsed”
with less water Select the methods of reduction Establish “base-line” water requirements for
current processes Alter water usage in rinse bath by various means Examine “Indicators” of
wafer cleanliness

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Manufacturing Peterson, et al. 19 Methods for DI Reduction Pulsed rinse baths –HF
chemistry –Piranha (H 2 SO 4 /H 2 O 2 ) chemistry Decrease in bath volume

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Manufacturing Peterson, et al. 20 Example Rinse Sequence: SCP 9400 tool Motorola MOS
12 Piranha Super Q Rinse HF SC1 IPA DRYER

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Manufacturing Peterson, et al. 21 Pulsing Experiments HF Chemistry 2 minutes in 10:1 HF 6
minute overflow “first rinse” @ 15 gpm 2 minute overflow “second rinse” @ 15gpm ** **
Other chemistry steps with “first rinse” baths could precede this step.

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Manufacturing Peterson, et al. 22 Experimental Variations HF Chemistry “First Rinse” time:
4, 5, 6 minutes “First Rinse” flow rate: 8 - 15 gpm “Pulsed” flow conditions –Period:10
seconds to 2 minutes –High Flow Time:1 second to 60 seconds Wafer loading: 1 to 50 wafers
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Manufacturing Peterson, et al. 23 Chemical Carryover Results HF Chemistry Pulsed flow
exhibits an improvement over conventional flow in terms of the volume of water employed to
obtain the same level of wafer cleanliness.

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Manufacturing Peterson, et al. 24 Pulsing Experiments Piranha Chemistry 10 minutes in 7.5:1
H 2 SO 4 / H 2 O 2 at 120 °C 5 “quick-dump rinses (“first rinse”) -3 hot water, 2 cold water -
High flow for ~1 minute, ~5 second drain, ~30 second refill -Flow rate ~ 15 gpm 2 minute
overflow “second rinse” @ 15 gpm ** ** Other chemistry steps with “first rinse” baths could
precede this step.

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Manufacturing Peterson, et al. 25 Experimental Variations Piranha Chemistry ~ 50
experiments conducted “First Rinse” utilized both quick dump and overflow modes “First
Rinse” time 3 - 9 minutes “First Rinse” flow rate 8 - 15 gpm “Pulsed” Flow conditions –
period:10 seconds to 4 minutes –high flow time:2 seconds to 2 minutes Hot and Cold Rinses
“Agitation” (using robot arm)

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Manufacturing Peterson, et al. 26 Effect of Pulsing and Quick-Dump Rinsing

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Manufacturing Peterson, et al. 27 Effect of Pulse “Sequence” “’On’ first” provides a
marginally more effective rinse due to the occurrence of convection before diffusion.

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Manufacturing Peterson, et al. 28 Effect of Temperature and Agitation Hot rinses and cold
rinses with agitation reduce the amount of carryover associated with a standard cold rinse.
This is possibly due to an increased rate at which chemical contaminants are swept from the
wafer surface.

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Manufacturing Peterson, et al. 29 Comparison: Carryover to Surface Loading Piranha
Chemistry “ Clean” Carryover: 0.01 mg H 2 SO 4 ==> 10 -7 moles Surface Measurements by
XRF: 10 13 molecules S/cm 2 For 50 200mm wafers ==> 10 -7 moles

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Manufacturing Peterson, et al. 30 Rinse Bath Volume Experiments Bath Comparison

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Manufacturing Peterson, et al. 31 Comparison of Rinse Tank Performance HF Chemistry,
Bare Wafers The lower volume tank exhibits an improvement over the standard tank in
rinsing bare Si wafers.

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Manufacturing Peterson, et al. 32 Comparison of Rinse Tank Performance HF Chemistry,
Oxide Wafers For oxide wafers, no significant difference is seen between the standard and
Dynaflow tanks.
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Manufacturing Peterson, et al. 33 Summary Under certain conditions, pulsing has a
pronounced effect on rinse efficiency. Combining pulsing sparingly with quick-dumps (in
those processes which allow for quick-dumps) can further increase rinse efficiency. A
substantial portion of the time during rinsing is spent “cleaning up the water” rather than
cleaning up the wafer surface. Moving the characteristic operating conditions of the rinse
tank closer to Plug flow conditions can potentially reduce water usage over that required for
CSTR conditions. A new rinse bath shape using less water volume can decrease water usage
while achieving an effective rinse for bare silicon wafers.