Design concept for a highperformance positive photoresist

Makoto Hanabata, Yasunori Uetani, and Akihiro Furuta

Citation: Journal of Vacuum Science & Technology B 7, 640 (1989); doi: 10.1116/1.584621
View online: http://dx.doi.org/10.1116/1.584621
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Published by the AVS: Science & Technology of Materials, Interfaces, and Processing

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 Design concept for a high-performance positive photoresist
Makoto Hanabata, Yasunori Uetani, and Akihiro Furuta
Sumitomo Chemical Co. Ltd.. Osaka Research Laboratory. 3-1-98. Kasugadenaka. Konohanaku.
Osaka City. Osaka 554. Japan

(Received 23 September 1988; accepted 15 March 1989)

An attempt was made to design a high-performance positive photoresist from the standpoint of
the image formation process. There are a lot of trade-off relationships among performance of a
positive photoresist. A study was made to raise performance without the decrease in other
performances. It was necessary to design a new type of novolak resin that has a molecular
structure different from the existing materials. Many kinds of cresol-formaldehyde type novolak
resins were synthesized and evaluated lithographically. Such items as molecular weight,
molecular weight distribution. isomeric structure of cresol, the position of methylene bond, and
the content of quinonediazide in a positive photoresist were investigated. Three methods were
found useful: (i) to apply high-ortho novolak resins that have a high content of ortho-ortho'
methylene bonds (ii) to optimize molecular weight distribution ofnovolak resins, and (iii) to
optimize the content of quinonediazides in a photoresist. These results are explained in terms of a
simple model for positive photoresist development, which we call "stone wall model". This model
is applicable to design a high-performance positive photoresist.

I. INTRODUCTION designing a high-performance positive photoresist that can

With the increasing density of very large scale integrated
(VLSI), submicron level fine patterns have come to be de-
manded. Accordingly. there is an increasing need for a high-
performance positive photoresist superior in sensitivity, film
thickness retention, heat resistance, and resolution capabili-
ty. Unfortunately. these aspects are usually balanced in var-
ious trade-offre1ationships. that is. one becomes worse when
another is improved (Fig. 1). A lot of attempts have been
made to improve performance of a photoresist; One of the
methods to raise sensitivity is to use additives that can pro-
mote dissolution rate in exposed parts of a photoresist. How-
ever. these additives promote dissolution rate also in unex-
posed parts. resulting in the decrease in film thickness
retention [Fig. I (a)]. To raise heat resistance. it is effective
to use high molecular weight novolak resins. However. in
this case. the resist sensitivity becomes worse because of the
low dissolution rate in an alkali developer of those resins
[Fig. 1(b)]. One of the methods to improve resolution capa-
bility is to develop a photoresist with a dilute alkali develop-
er. This method also decreases resist sensitivity because the
dissolution rate becomes low [Fig. 1 (c)].
The purpose of this work is to find a new concept for
escape from these trade-off relationships.
Figure 2 shows the image formation process in novolak-
quinonediazide photoresist systems. In exposed parts, quin-
onediazides are converted to indene-carboxylic acids and
dissolve in alkali developer with novolak resins. On the other
hand, in unexposed parts, quinonediazides make novolak
resins insoluble by acting as a dissolution inhibitor. Figure 3
illustrates the dissolution rate diagram of a positive photore-
sist system. Rn is the dissolution rate of the novolak resin
used in the positive photoresist. Rp is the dissolution rate of
exposed parts and Ro is the dissolution rate of unexposed
parts of the photoresist. A large value of Rp means high
resist sensitivity and a small value of Ro means high film
thickness retention. In order to improve resolution capabili-
ty. it is necessary to raise Rp (dissolution promotion) and/
or to lower Ro (dissolution inhibition). In other words, reso-
lution capability depends greatly on the ratio of Rp to Ro.
that is, a high Rp/Ro ratio corresponds to a high y-value.
The large discrimination between Rp and Ro is preferable for
a high-performance positive photoresist.
There are two main components in this system-novolak
resin and naphthoquinonediazide (NQD). In the present
work, we have studied on the novolak resin at the fixed

c:
.2
cIII
;f---
~
a;
a:

~
I:R
III
c:
.!::!
.c
j"/i
, 0
. ~
>:-
III
u
C
0
Vi
'iii
III
0:
I
/"/
:'
~ 0
, </
.;:
I :0
8.
8
.~
":5
l'
:
,:
>:-
. ~tS"
4#
#Q
FIG. I. Trade-olfrelationships among various
performances of a photoresist (- - ~ ) means

.
the improvement of the performance .

l_~~
•0
I-
g : J>""
.....~ ~III .",,(5
be
.§ J: 0:
u::
,,~
Sensitivity Sensitivity Sensitivity

640 J. Vac. Sci. Technol. B 7 (4). JullAug 1989 0734-211X/89/040640-11$01.00 © 1989 American Vacuum Society 640

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 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 641
641

rg:(Exposed part)

IiI i\:. ~':;")!?'< '=''27~

0 "
(1) Molecular Weight

(2) Isomeric Structure of Cresol

0H

+-CtCHZ-1;;
CHJ

""""".:'.~

(Unexposed part) (0)

OCHJ
(m)
6OiJ
(p)

(3) Methylene Bond Position

Oil
FIG. 2. Image formation process in a novolak--<juinonediazide photoresist
system.
(01 >if. yCHz+
OH ()i CH
NQD. The structure of NQD is also important, but this fac- ,., +Q;:+ ~+~,
tor was not varied in this work.
Figure 4 shows four factors of novolak resins that can
influence the materials and lithographic performance.
The first is molecular weight. Novolak resins are synthe-
(p) t-6 +
elll
CHZ

sized through addition-<:ondensation reactions of cresols

with formaldehydes. In proportion to the degree of the reac-
tion, novolak resins that have various molecular weight are
obtained. The second is isomeric structure of cresols. There
are three isomeric structures in cresols: orthocresol, meta-
cresol, and paracresol. The third factor is methylene bond
position. In the addition-<:ondensation reaction, methylene
bonds are formed between two cresol units. There are three
positions for a methylene bond: two ortho positions and one
para position. A methylene bond can only be formed at two
of the three positions. Consequently, several kinds of methy-
lene bond structure are present as shown in Fig. 4.
We have previously reported l the effects of molecular
weight, isomeric structure of cresol, and methylene bond
position on resist sensitivity, film thickness retention, and
heat resistance.
There are two more factors to be considered; The first is
molecular weight distribution-the fourth factor of novolak
resins. It is known that the molecular weight distribution of
polymers plays an important role in resist performance of
negative photoresists like bis-azide/rubber systems. On the
other hand, very little is known about the infiuence of this
factor on the performance of positive photoreslsts. The sec-
ond is the content of quinonediazide compounds in a photo-
resist-the fifth factor.
(Exposed parts)
(4) Molecular Weight Distribution
FIG. 4. Four factors of novolak resins.
In the present work, we measured the dissolution rates
(Rn ,R o' and Rp ) of photoresists containing various kinds of
cresol-formaldehyde novolak resins and investigated the in-
fluence of these five factors on resist performance (sensitiv-
ity, film thickness retention, heat resistance, and resolution
capability). On the basis of the experimental results, we will
discuss the design concept for a high-performance positive
photoresist. Finally, we will propose a new model for posi-
tive photoresist development.
II. EXPERIMENTAL
A. Materials
Materials used for composing photoresists are shown in
Fig. 5.
1. Novolak resins
Table I list the novolak resins used in this experiments.
These resins were synthesized under various conditions in
usual manners. 2 •3 The feed ratios of metacresol/paracresol
and cresol/formalin were changed. The catalysts used were

Rp
tal (bl
o
Rn R0-Q-~-o
RO OR

~
Resin (Unexposed
parts )

Ro

Resin. OU'---""'·
NavoIak I, """'J1QZ ide
FIG. 5. Stucture of samples used in this experiment. (a) Novolak resin. (b)
FIG. 3. Dissolution rate diagram of a positive photoresist system. NQD (~aphthoguinone diazide).

J. Vac. Sci. Techno!. B, Vol. 7, No.4, JullAug 1989

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 642 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 642

TABLE 1. Characteristics of novolak resins used in this experiment. (A) (8)

Feed ratio
Sample metacresol
No. paracresol

A 8 2 6750
B 8 2 8410
C 8 2 11660
D 8 2 14500 C-2 C-4
C-2
E 8 2 17950 C-6 C-4
F 10 o 8500 C-6 C-2
G 6 4 8200
H 5 5 8320
I 4 6 8020 '-6
J 10 o 12 9800
K 10 o 29 10 150 C-4

L 10 o 33 10020
M \0 o 42 9850
N 10 o 46 9750
o 10 o 16200 5400 3.00
P 10 o 16 150 3550 4.55
Q 10 o 16 170 2880 5.61
R 10 o 16 180 2400 6.75
FIG. 6. "C-NMR spectra of novolak resins that have different methylene
bond struct ures.

which the methylene bonds are highly formed at ortho posi-

oxalic acid and organic salts of divalent metals such as tions of cresols.
Ba,Mg, Mn, Zn, and Cd.
3. Quinonedlazide
2. Analysis of novolak resins
Quinnonediazide compound used in this experiment
Molecular weight was measured using gel permeation (NQD) was synthesized from 2,3, 4-trihydroxybenzophen-
chromatography (G PC) and is presented as the polystyrene one and I, 2-naphtoquinonediazide-5-sulfonyl chloride
equivalent value. The GPC solvent was tetrahydrofuran. (molar feed ratio = j).
The structure of novolak resins concerning methylene
bond position was measured using IJC_NMR spectroscopy. B. Resist preparation
In this measurement, the INEPT method introduced by
Resist solutions were prepared through mixing novolak
Morris and Freeman 4 gave use useful information upon the
resins with NQD and solvent (ethylcellosolveacetate) in the
aromatic carbon atoms. We paid attention to the ratio of
fixed ratio. After that, they were filtered through O.2-/lm-
"unsubstituted" carbon atom in the benzene ring represent-
membrane filters.
ed as Sn.
Sn value was determined as follows:
(i) First, IJC-NMR spectrum of metacresol was mea-
c. Wafer processing condition
sured, and the correction factor fn (n = 2,4,6) was calculat- The wafer processing condition used for lithographic eval-
ed from the peak area of Con (n = 2,4,6) carbon atoms. uation is shown in Table II.
fn = an/as,
D. Measurement of dissolution rates
where an is the peak area of C-n carbon atom. fn is the ratio
The following three bulk dissolution rates were measured
of peak area of C-n atom to that of C ~ s atom.
on a Perkin-Elmer development rate monitor (DRM).
(ii) Next, DC-NMR spectrum of a metacresol novolak
resin was measured. The peaks of un substituted Con atom
TABLE II. Wafer processing conditions used for lithographic evaluation.
are enhanced through INEPT method. Sn(n = 2,4,6) was
defined as the ratio of unsubstituted Con atom and given by; Wafer : 4-in. silicon wafer
Sn = (An X lOO)/(Asxfn) Resist coating : 4000 rpm120 s
Resist thickness : -1.30 Itm
where An is the peak area of un substituted Con atom andfn Prebake : 90 'C/20 min in convection oven
is the correction factor calculated in (i). Exposure ; Nikon NSR 1505G3C (N.A. = 0.42)
In this treatment, it was assumed that C~s atom is not Development : Puddle, 23 'C, 60 s
Developer ; 2.38% Tetramethyl
substituted because a position meta with respect to an OH
ammonium hydroxide
group is usually inactive in a condensation reaction. Rinse : Pure water, 60 s
Figure 6 shows the spectra of novolak resins that have Film thickness : Nanospec
different bond structures. With increasing S4 value, type (B) measurement
structure increases, namely, high-ortho novolak resins, in

J. Vac. Sci. Technol. e, Vol. 7, No.4, JullAug 1989

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 643 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 643

( 1) Rn: dissolution rate of novolak resins

Novolak resin solutions without NQD were spin coated 170

onto silicon wafers and prebaked. The dissolution rate in the 160
developer was measured without irradiation.
;:
(2) Ro: dissolution rate of unexposed parts of a photore- 'uc" 150
.9
\II
sist. .~
0::
140

(3) Rp: dissolution rate of exposed parts of a photoresist 130

~
where the exposure dose is 60 mj/cm 2 • :x:
120

E. Evaluation of heat resistance

5 10 15
The developed wafer was kept in a convection over for 30 MO\~cU\or W~ight

min. Heat resistance of a photoresist was defined as the tem-

FIG. 8. Effect of molecular weight of novolak resins on heat resistance.
perature just before the heat deformation of resist images
begins. The resist images were observed with scanning elec-
tron microscope (SEM).

III. RESULTS AND DISCUSSION B. Effect of Isomeric structure of cresol

A. Effect of molecular weight of novolak resins 1. Dissolution rate
t. Dissolution rate Figure 9 is the result when metacresol/paracresol feed
ratio was varied from Wto ~ under the condition of similar
Figure 7 shows the relationship between molecular weight
molecular weight (8000-8500). The novolak resins used
ofnovolak resins and dissolution rates (Rn,Rp,R o )'
here were Band F-I in Table I.
The novolak resins used here were A-E in Table I.
The incorporation of the para component has the effect of
With increasing molecular weight, both Rp and Ro de-
decreasing the dissolution rate ofnovolak resins (Rn ) great-
crease. This is because the dissolution rate of novolak resins
ly, which causes the decrease in Rp and Ro. We believe that
(Rn) decreases with the increase in molecular weight. Since
this large dependence of R n on meta/para ratio is attributed
the degrees of decrease in Ro and R p are almost the same, the
to the difference of polymer structure (regularity or ran-
Rp/Ro ratio does not change appreciably depending on mo-
domness of cresol unit sequence in polymer chain) among
lecular weight.
novolak resins having different meta/para ratios. Paracresol
units can be regarded as giving polymer chains regularity or
2. Heat resistance
rigidness, because the methylene bond is formed at only
Figure 8 shows the molecular weight dependence of heat ortho positions in paracresol. On the other hand, in metacre-
resistance of photoresists. Heat resistance was improved sol, since the methylene bond can be formed either ortho
with increasing molecular weight of the novolak resin. This position or para position, the polymer chain will have ran-
is probably due to the rise of the softening point of novolak
resins.

,01 103

-0-.
1
Rp
------ e--~
1(f rJ.

u Rp
'" -%
f
~1a2
~
<:
C
~
~
102 .: 10
(11

Ci
'
101

'Q Rp' 0:

~
(11
0 c
cr Q
"5
,
'0.
'0
~'0' 10
'
~
10°
j \,.. PQ
0

1~~~--~~--L-~
5 10 15 20 (x )
Molecular Weight
Xl/O ¥.2 60. % 2Al 010
met9Paro ratio

FIG. 7. Effect of molecular weight of novolak resins on dissolution rates. FIG. 9. Effect of isomeric structure of cresol on dissolution rates.

J. Vac. ScI. Technol. B, Vol. 7, No.4, JullAug 1989

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 544 Hanabata, Uetani, and Furuta: Design concept for a photoresist 644

domness and flexibility. The greater steric bulk surrounding

the -OH group in the p-cresol groups (as compared to the m-
cresol isomers) may playa role in modifying polymer base
solubility.
Ro was found to vary by over a factor of 1O~ compared
with 10 1 of Rp variation when meta/para ratio was varied
from if to~. The reason why the degree of decrease in Ro is
much larger than that in Rp with the increase in meta/para
ratio is probably that the dissolution promotion effect of in-
dene-carboxylic acid is prominent particularly in paracom-
ponent rich matrix which has more regular or rigid polymer
structure.
Consequently, Rp/Ro ratio increases with increasing
pararatio.

2. Heat resistance
The improvement in heat resistance was observed with the
increase in paracresol ratio (Fig. 10). This result can also be
interpreted in terms of the increase in regUlarity or rigidness
of polymer chains.
FIG. II. Effect of methylene bond position on dissolution rates.

c. Effect of methylene bond position

1. Dissolution rate
Figure 11 shows the dependence of dissolution rates on S4
value in metacresol novolak resin (J-N) systems. With in-
creasing S4 value, Rn decreases slightly, but Ro decreases
greatly. This indicates that the dissolution ofnovolak resins
is strongly inhibited in unexposed parts in high-ortho novo-
lak resin systems. On the other hand, S4 value shows little
effect on Rp in exposed parts. As a result, Rpl Ro ratio in-
creases with increasing S4 value. These results indicate that
the high-ortho novolak resin systems can reduce the dissolu-
tion rate predominantly in unexposed parts. Bender et al. 5 •6
measured the cure rate of dihydroxydiphenylmethane
(DPM) in the reaction with hexamethylenetetramine
(HMT A) and found the unusually rapid cure rate of 0-0'
materials compared with other isomers (Table III). The
accessability of the "vacant" para position is regarded as
enhancing cure rate owing to its high electron density.
150
Keeping this fact in mind, we propose a new dissolution
inhibition model in unexposed parts prominent particularly
in high-ortho novolak resin systems, that is, dissolution inhi-
bition due to azocoupling reaction between novolak resins
and quinonediazide (Fig. 12). High-ortho novolak resins
have a lot of vacant para positions compared with "normal"
novolak resins (Fig. 13). Those positions can enhance the
electrophilic azocoupling reaction, which inhibits the diso-
lution of novolak resins to the developer. An azocoupling
reaction is usually catalyzed by a base. In the image forma-
tion process of photoresists, alkali developers can be regard-
ed as catalyzing the reaction.
2. Heat resistance
The decrease in heat resistance with the increase in S4
value as shown in Fig. 14 can be explained as roIlows; the
normal novolak resins probably have high softening points
compared with high-ortho novolak resins, because the nor-
mal novolak resins the higher content of para-para' methy-
lene bond than high-ortho resins as shown in Fig. 13. This is
understandable from Table III, where DPM which has

140 TABLE III. Reactivity of dihydroxydiphenylmethane (DPM) with hexa-

}.l
methylene-tetramine (HMT A) according to Bender et al.'
<Ii 130
u
c:
.9 Gel time with 15'. HMTA Melting
Ul Structure of OPM
.~
120 (sec) Point("C)
a: OH OI-t

]
:r:
110
0-0'
Cr z'6 CH
60
11a5
-119.5
100 OH OI-t
119
1%
1.. . I

8-1 6'1;
.J

4.g
o_p'
OC~~ 240 -120
OH OI-t
metg.... ratio 162
'1Xl ra p-p' 175
QCHZ.Q -163
FIG. 10. Effect of isomeric structure of cresol on heat resistance.

J. Vac. Sci. Technol. B, Vol. 7, No.4, JullAug 1989

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 645 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 645

,...----0- - -----,
;OCtz
I I

: S02
, \ I
• 0
: 0 p"'-O:+
I
FIG. 12. Dissolution inhibition model due
I C I to azocoupling reaction between novolak
I I
I 0 I resins and quinonediazide.
'...('
:~-
I
I
0 I
I
I

: S~ :
(soluble)
lNOO
: 2 0
,
.... _--- ----_.. -----• I

para-para' bond shows the highest melting point among
three isomers.
D. Effect of molecular weight distribution of novolak
resins
1. Dissolution rate of novolak resin (RnJ
Figure 15 shows the development profiles of novolak res-
ins that have various MwlMn values. The dissolution rate
depends on the film thickness dissolved; The rate near the
surface of the film was Jow compared with that of the bulk.
The rate increased with the film thickness dissolved and be-
came constant in the bulk of the film. The last 0.1 - O. 2 Jim
near the bottom dissolved slowly, probably because of the
adhesion to the silicon surface.
It is notable that the dissolution rate in the bulk depends
highly on MwlMn values of novolak resins. On the other
hand, the dissolution rates near the surface are not very dif-
ferent among four samples. These results can be interpreted
as follows: The novolak resins with large MwlMn values
contain much more components of low molecular weight
novolak resins than novolak resins with small MwlMn val-
ues. Figure 16 shows the illustrations ofnovolak resins, (a)
is a novolak resin with small MwlMn value and (b) is a
novolak resin with large MwlMn value. H, M, and L mean
high, middle, and low molecular weight component, respec-
tively. Low molecular weight components generally have
higher dissolution rates than high molecular weight compo-
nents. Arcus has reported 7 that the log of dissolution rate is
linearly related to the log of the molecular weight ofnovolak
resins. Consequently, these low molecular weight compo-
nents dissolve rapidly to the developer before high molecular
weight components begin to dissolve. This increases the sur-
face area of high molecular weight components which are in
contact with the developer, leading to the dissolution pro-
motion of high molecular weight components.
We believe that such a dissolution promotion effect is
prominent particularly in the bulk of the film. Figure 17
shows the illustration of the novolak resin film being devel-
oped; At the initial stage of development (a), the novolak
film begins to dissolve from top of the film. In this stage, the
surface area is relatively small. At the middle stage of devel-
opment (b), the surface area of resins greatly increases, be-
cause low molecular weight components dissolve much fas-
ter than high molecular weight components. This is the
reason why the dissolution rate in the bulk of the film is
higher than that of the surface as shown in Fig. 15.
2. Dissolution rate of photoresist (Rp.RoJ
Figure 18 shows the dissolution inhibition effect of NQD.
Dissolution rate in unexposed parts of photoresists (Ro) is
plotted against NQD/novolak ratio for novolak resins that
have various MvJMn values. The log of Ro decreases linear-
ly related to NQDI novolak ratio. It is marked that the de-
gree of the inhibition effect depends on MwlMn values (The
170
~160
QJ

~ 1:Q
.~ FIG. 14. Effect of methylene
&l1JJ bond position on heat resis-
tance.
11 1:J)
(al J:
120

FIG. 13. Comparison of polymer structure between (a) high-ortho novolak

resin and (b) normal novolak resin .• vacant para position ..... 0 vacant
artha position.

J. Yac. Sci. Techno!. B, Yol. 7, No.4, Jut/Aug 1989

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 646 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 646

n (surface) (bulk)
01 (al (bl

{SUrfoce)~EJ
.~.t~la:·U
103 <;

• •
• ••
~n= 6.7Srf'
f
c
1

• • •
(bulk I

(bottom) -+
Resin

'"
& 5.61~
c FIG. 17. Illustration of novolak resin film being developed (a) initial stage
0
"5 4.55
~
is
3.00,.J'
05 1.0 1.5
0
Film thickness dissolved
()Jm)
FIG. 15. Development profiles of novolak resins having various MwIM"
values.
degree of the inhibition effect corresponds to the slope of the
line in Fig. 18). With increasing MjMn value, the slope
becomes steeper, having the maximum at -5-6 of MwlMn
value. After that, the slope becomes gentle. As a result, the
line 0 crosses the line P at - 20/100 ofNQD/novolak ratio.
Figure 19 is the GPC traces of a typical photoresist for
"before" and "after" development. We measured this phe-
nomenon according to the following procedure; First, we
coated two silicon wafers with photoresist and prebaked
them. (The thickness was -0.1 jLm). Next, we developed
one of the wafers without irradiation. No film thickness loss
was observed. After that, we dissolved both films to tetrahy-
drofuran and measured molecular weight change. The two
weight fraction data are normalized at the first peak in Fig.
19.
It is apparent form Fig. 19 that, after development, the
weight fraction of lower molecular weight components in-
creased compared with that of higher molecular weight
components. We believe that this increase in weight fraction
is due to the products of azocoupling reaction between novo-
lak resins and quinonediazides as shown in Fig. 12.
Figure 19 indicates that the low molecular weight compo-
nents are more reactive than high molecular weight compo-
nents in the azocoupling reaction. This is understandable
Siliron
of development and (b) middle stage of development.
from the fact that the small molecules are generally more
2D 2.5
mobile and reactive than large molecules.
The dependence of Ro on M wiMn values in Fig. 18 can be
explained as follows: The dissolution of unexposed parts are
highly inhibited in photoresists which contain novolak res-
ins with large M wiMn values, because those resins contain a
lot oflow molecular weight components. However, too large
an amount of low molecular weight components decreases
the inhibition effect, because low molecular weight compo-
nents remaining unreacted with NQD adversely enhance the
dissolution. In this case, much more NQD for azocoupling
reaction is needed to inhibit the dissolution. Consequently,
there is an optimum MjMn value for the inhibition effect.
In Fig. 18, the optimum value is - 5-6.
Figure 20 shows the effect of MwlMn values on dissolu-
tion rates at the fixed NQD/novolak ratio (30/100). Ro was
plotted from the dissolution rate in the bulk of the film in
Fig. 15. It increases proportionally with MjMn value. Rp
also increases with MwlMn value because Rp is generally
parallel to Rn' This agrees with the results shown in Fig. 15.
As a result, RplRo exhibits a maximum at -5 of MwlMn
value.
o ~n= 3.00
p 4.55
o 5.61
R 6.75

(al (bl

~ MM MMJ

. . De-.<elopment
~ H
L

~
M
L

... Devebpment

00 8 8] [)
~8
M®
'"'
\6
HLPc89
162' - - - - ' - - - " - - - . . . . . J - - - ' - - - -
If) ~OO lrOO ~OO ~OO 4~OO
NQo/Novolak
FIG. 16. U1ustration of novolak resins (a) novolak resin with small M".1 M"
value and (b) novolak resin with large M".IM" value. FIG. 18. Dissolution inhibition effect of NQD.

J. Yac. Sci. Technol. B, Yo I. 7, No.4, JullAug 1989

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 647 Hanabata, Ueta"l, and Furuta: Design concept for a photoresist 647

Molecular weight Mw = -16.000

ZJ11IJ
I
170
N~ =~
NovoIak 100
160
~
r-----Azoa:JUplirg products j 150

~
.!!1
~ 140
a::
£
:r
130

'.~JJ
120

-.l____1 -___L .....

3 4 5 6 7

Quinonediazide
FIG. 21. Effect of molecular weight distribution of novolak resins on heat
resistance.

---.".) Ve
- before}
dENelopment
-- aft er
FIG. 19. GPe traces of a typical photoresist; -before development. -after
development.
3. Heat res/stance
Figure 21 shows the effect of MwlMn value on heat resis-
tance of photoresists. With increasing MwlMn values, the
heat resistance becomes higher and reaches the maximum at
-5.5 of MwlMn value. After that, it becomes low.
With increasing Mwl Mil value, both high molecular
weight and low molecular weight components increase un-
der the condition of similar molecular weight. An increase in
high molecular weight components raises the softening point
of novolak resins. On the contrary, an increase in low molec-
ular weight components lowers the softening point. The re-
sult in Fig. 21 can be interpreted as follows: In the region of
the relatively small Mwl Mil value, the effect of the increas-
ing the high molecular weight components improves heat
resistance. However, when the M wiMil value becomes much
larger, the effect of the increase in low molecular weight
components lowers heat resistance. As a result, there is an
optimum Mwl Mil value where these two effects balance. It is
-5.5 in Fig. 21.
We think the increase in high molecular weight compo-
nents gives a resist image "framework" that protects the heat
deformation of resist images. We also believe that the in-
crease in low molecular weight components breaks this
framework through melting or softening upon heat treat-
ment.
E. Effect of the content of quinonediazide in
photoresists
1. Dissolution rate
Figure 22 shows the effect of NQD/novolak ratio on dis-
solution rates at the fixed MIL,! M n value (4.55).
With increasing NQD/novolak ratio, Ro decreases be-
cause of the dissolution inhibition effect of NQD as seen in
Fig. 18. On the other hand, Rp increases gradually and

l°l I
N~10k =~
100
I
",rr:-..
104 ..... ,,.-----

~n =455
.
--,---- .-
i
iO~

103 lcr 10 3

~102
E..
102

~ ~
c
~ 102
1:
r'
'"
~ X)1
,~
'0
' '" 101
&
.5:; .....~.o Rn
.~
i
0
.ey-
lcP
i
0
10° 1&

-I
10 1
16

i}
3 4 5 6 7 162
19(,
~n 100 29ro ~ ~
FIG. 20. Effect of molecular weight distribution of novolak resins on disso- NQ~I\IC7.OOk
lution rates. FIG. 22. Effect of NQD/novolak ratio on dissolution rates.

J. Vac. Sci. Technol. S, Vol. 7, No.4, JullAug 1989

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 648 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 648

-- "--T' ···---l
" 2. Heat resistance
170
Mw= 16.150 Figure 23 is the relationship between NQD/novolak ratio
~100 ~= 4!;.f5 and heat resistance of photoresists. With increasing NQD
p
~15O

~ 1L.O
1 content, heat resistance is greatly improved.
NQD is converted to indene-carboxylic acid via a ketene
intermediate as shown in Fig. 2 under heat treatment as well

~
.~

a: 1~ as upon irradiation. The ketene intermediate will act as

g "crosslinking" agent between polymer chains of novolak
r 12!T_.
.1. •... J.. _ t.._
Y'1OO ~oo ~oo
NO%ollOlak
FIG. 23. Effect ofNQD/novolak ratio on heat resistance.
reaches a maximum. After that, Rp begins to decrease.
These results are explained as follows: At the small NQDI
novolak ratio (10/100-20/100), the indene-carboxylic
acids formed upon irradiation promote the dissolution of
exposed parts and raise Rp. When the NQD/novolak ratio
increases further, the amount of undecomposed NQD in-
creases even in exposed parts, because the exposure does was
fixed at 60 rnj/cm 2 in this experiment. Such an undecom-
posed NQD will inhibit the dissolution of exposed parts and
lowers Rp. As a result, Rp has the maximum at a certain
NQD/novolak ratio. It is -30/100 in Fig. 22. RplRo ratio
increases monotonically with the increase in NQD/novolak
ratio, because the degree of decrease in Ro is much larger
than that in Rp even at a large NQD/novolak ratio.
resins through esterification reaction and will raise the mo-
J •...• 1
lecular weight of resins. We think this is the main reason for
% the improvement of heat resistance.
Another explanation for the improvement of heat resis-
tance can be given by the increase in azocoupling reaction
between NQD and novolak resins with the increase in NQD
content. The azocoupling reaction can be regarded as the
crosslinking reaction, because NQD has three quinonedia-
zide groups and acts as a crosslinking agent. Such a reaction
will also raise molecular weight of novolak resins in photore-
sist and will improve heat resistance.
F. Relationship between factors of novolak resins
and resist performance
Table IV summarizes the effects of five factors of novolak
resins on dissolution rates (Rp ,Ro) and resist performance.
Generally, Rp,R o, and Rpl Ro ratio correspond to sensitivity,
film thickness retention, and resolution capability, respec-
tively.
Figure 24 shows the dissolution rate diagrams which show
the influence of factors of novolak resins. In Fig. 24, (a) is
the original relationship among Rn ,R o, and R p' (the same as
Fig. 3). To improve the performance of photoresists, Rp

TABLE IV. Effects of five factors ofnovolak resins on dissolution rates and resist performance: (0): improvement, (x): deterioration, (1): increase, (j):
decrease, and ( - ): no variation.

Disolution Rate
unexposed exposed
RpRo Film thick. Heat
Factors (Rp) R" Ratio Sensitivity retention resist Resolution

Molecular (0) (0)

weight I I j

MW:! (0) (x) (x)

Isomeric (0) (0) (0) (0)

structure j j j
of cresol (0) (x) (x)
para:!

Methylene (0) (O) (O)

bond position j I
S.:! (0) (x)

Molecular (x) (0) (0) (0) (0) (0) (0)

weight ,,/, /,,, /,,, /,,, /'\.
Distribution (0) (x) (x) (x) (x)
M.,IM.:!

NQD/Novoiak (0) (0) (0) (0) (0) (0)

ratio: 1 j /,,, /,,,
(0) (x) (x)

J. Vac. ScI. Technol. B, Vol. 7, No.4, Jull Aug 1989

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 649 Hanabata, Uetanl, and Furuta: Design concept for a photoresist 649

(&posed parts) Rp When NQDI novolak ratio increases, R" does not
Rp change, but Ro decreases. Rp increases when NQD/novolak
(0) (b)
ratio is relatively small [(i) in (h)], but decreases when the
ratio increases further [® in Fig. 24 (h)]. Therefore, an
optimum NQD/novolak ratio is present.
hi As a result, Figs. 24 (d), 24 (g), and 24 (h) are three
useful methods for improving photoresist performance.
,=,.~

G. Stone wall model for positive photoresist

Rp
development
Rp
t On the basis of the results and discussion described above,
Rn Rn
we will propose a new model for positive photoresist develo-
pement, which we call the stone wall model. This model is
illustrated in Fig. 25.
High molecular weight novolak resins (H), low molecu-
lar weight novolak resins (L), and naphthoquinonediazide
(N) constitute a photoresist film. We imagine this as stone
wall, because the relatively small Land N molecules seem to
Rp fill in blanks among large H molecules. In Fig. 25, the poly-
mer chains are depicted as being globular for the sake of
convenience but they are expected to be quite intertwined in
resist films.
In exposed parts of photoresists, the indene-carboxylic
acids formed upon irradiation and low molecular weight no-
volak resins dissolve to the developer before high molecular
weight novolak resins begin to dissolve. This increases the
surface area of high molecular weight novolak resins and
enlarges contact area with the developer, leading to the dis-
solution promotion of the photoresist films.
In unexposed parts, the azocoupling reaction between low
molecular weight novolak resins and NQD dominates the
dissolution of photoresists to the developer. In other words,
the azocoupling reaction products prevent the stone wall
from being broken by the developer (dissolution inhibition).
The stone wall model gives us a clue to design a high-
FIG. 24. Dissolution rate diagrams which slow the influences of factors of
novolak resins.

(f) ®
should be high and Ro should be low (b). There are two
methods for this-(c) and (d). ~
GJ @<o
~
When molecular weight of novolak resins is raised, R n ,
Ro, and R p decrease as shown in Fig. 24 (e). ~ ~@GI@to3H
When the metacresol/paracresol ratio increases, these
three rates decrease as in Fig. 24 (e), but the degree of de- '---..~~~
H'~ ~
crease in Rp is much smaller than that in R o, because the t:
dissolution promotion effect of indene-carboxylic acid HC@
formed in exposed parts is prominent particularly with the
increase in paracresol unit. This is shown in Fig. 24 (f). (u~
When S4 value is raised, only Ro decreases as shown in Fig. ~(/f!}~
24 (d) because the dissolution inhibition due to azocoupling
reaction in unexposed part is enhanced ony in unexposed H: High l'T'deo..I\arweght
rovolak resin
parts. L: Low "
When the molecular weight distribution of novolak resins
N: NQD (Naphtt-oquinore-
Azocoupling
becomes broad, Rn and Rp increase. Ro decreases when diazide )
MjMn value is relatively small (i) in Fig. 24 (g)], but in- reaction
crease when M wi Mil value becomes much larger [® in (g) ]. product
Consequently, there is an optimum MwIM" value. FIG. 25. Stone wall model for positive photoresist development.

J. Vac. ScI. Technol. S, Vol. 7, No.4, JullAug 1989

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 650 Hanabata, Uetanl, and Furuta: Design concept for a photoresist
performance positive photoresist. There are four main per-
formances required for a positive photoresist: sensitivity,
film thickness retention, heat resistance, and resolution
capability. As described in Sec. III D2, resolution capability
is highly influenced by low molecular weight novolak resins,
because these components promote dissolution in exposed
parts and inhibit dissolution in unexposed parts.
On the other hand, we believe that the high molecular
weight novolak resins affect the sensitivity, film thickness
retention, and heat resistance, which are usually in trade-off
relationships.
IV. CONCLUSIONS
A new design concept for a high-performance positive
photoresist was obtained. There are three methods to im-
prove resist performance with no or little decrease in other
performance:
(i) to apply high-ortho novolak resins, (ii) to optimize
molecular weight distribution ofnovolak resins, and (iii) to
optimize the content of quinonediazides in a photoresist.
These results are explained in terms of the dissolution pro-
motion effect in exposed parts and the dissolution inhibition
effect in unexposed parts.
J. Vac. Sci. Techno!. e, Vol. 7, No.4, JullAug 1989
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650
Finally, the stone wall model is consistent with these find-
ings and is applicable to design a high-performance positive
photoresist.
ACKNOWLEDGMENTS
The authors would like to acknowledge the support of
many co-workers in Osaka Research Laboratory. We also
acknowledge H. Moriguchi in Takatuki Reseach Laborato-
ry for I3C-NMR measurement. This paper was presented in
part at the SPIE's Symposium on Microlithography, Santa
Clara, CA, 1988.
A. Furuta, M. Hanabata, and Y. Uemura, J. Vac. Sci. Techno!. B 4, 430
I
(1986).
2Kirk-Othmer Encyclopedia o/Chemical Technology, 3rd ed. (Wiley, New
York, 1982), Vol. 17, p. 384
'A. Knop and W. Scheib, Chemistry and Application 0/ Phenolic Resins,
(Springer, New York, 1979).
·G. A. Morris and R. Freeman, J. Am. Chern. Soc. 101,760 (1979).
~H. 1. Bender, A. G. Farnham, J. W. Guyer, F. N. Apel, and T. B. Gibb,
Ind. Eng. Chern. 44, 1619 (1952).
°A. Knopand 1. A. Pilato, Phenolic Resins (Springer, New York, 1985), p.
49.
7R. A. Arcus, SPIE Proc. 631, 124 (1986).