Appendix

C4

Estimation of HSP from Solvent Mixtures

Table C4-5 HSP Optimization with PR2 Photoresist

Correctly Located
Solvents

Optimized
Solution
Time, min

<0.5

RO

d Disperse

d Polar

d H Bonding

DF

MPa

GOOD
& IN

BAD
& IN

GOOD
& OUT

9.45

20.67

8.82

5.90

1.2382 10

62

<1

10.09

20.19

8.56

7.64

1.0530

69

<2

15.05

22.33

5.97

2.71

1.0688

72

<5

19.10

24.31

2.94

3.58

1.0552

72

>5

24.54

22.33

10.44

6.11

1.0000

81

comparable to Table C4-1 was prepared. A summary of

results from that spreadsheet is shown in Table C4-5. The
spreadsheet is not shown here.
The HSP for PR2 should be taken to be that determined
by optimization with a solution time of no more than 1
minute. That is somewhat inferior to the one based on
a solution time of no more than 30 seconds. Reasons for
this selection are: a substantially better desirability factor
(DF), and fewer outliersdBAD and IN or GOOD and
OUT.
Yet, once the HSP for the soil are chosen by optimization, one is free to choose any solvent or mixture which
meets any local criteria, including presence or absence of
SHE concerns, or solution time.
These results clearly show how polymers with common
or similar structural elements (monomers) dont necessarily perform identically in solvent cleaning work. PR2 is
not PR1. It isnt just that PR2 is more easily cleaned than
PR1dthough there are at least three times as many solvent
combinations which remove PR2 in 30 seconds or less than
do PR1. Its that:


BAD
& OUT

Incorrectly Located
Solvents

PR2 has substantial levels of hydrogen bonding

intermolecular force, and PR1 apparently has
practically none. This makes PR1 a unique structure.
There is an analog with solvents. Perchloroethylene
has little or no hydrogen bonding intermolecular
forces because it has no hydrogen atoms. Its a unique
solvent.
HSP technology produces somewhat fewer
unpredictable outcomes for PR2 rather than PR1

598

(Table C4-5). Figures 3.38 and 3.39 enable another

viewpoint about this slight difference.

I. RATE PROCESSES
Solubility parameters are thermodynamic quantities
(Chapter 2.9.2), properties which are characterized by
equilibrium. As such, one wouldnt expect them to be
determinative of rate processes such as rate of dissolving.
However, it is clear from Tables C4-1, C4-2 and C4-5 that
the experimental measurements are of time to dissolve, and
for PR1 and PR2 that time does correlate with radius of
the solubility sphere. A smaller solubility sphere is noted
when the solution time is short, and the reverse is noted as
well.
One should not expect this to be a universal nding. It
occurs here because time to dissolve was used as a proxy for
whether or not the polymer dissolved. It occurs with these
experiments because the experimenters had used HSP to
select solvents and mixtures, some of which should be
successful, and time of solution was a practical way of
differentiating among them.

Endnotes
A.

Kesters E, Claes M, Le QT, Barthomeuf K, Lux M, Vereecke G,

Durkee JB. Selection of ESH Solvents for the Wet Removal of
Post-Etch Photoresists in Low-K Dielectrics Integration. Presented at
the MicroEngineering Conference, April 2008.