M I G R O ~

ELSEVIER Microelectronic Engineering 46 (1999) 375-378

Process optimization of a chemically amplified negative resist for electron beam exposure and
mask making applications

E. Ainley 1, K. Nordquist 1, D. J. Resnick 1, D.W. Carr 2 and R.C. Tiberio2

IMotorola
2100 East Elliot Road, Tempe, Arizona 85284 USA

2Comell Nanofabrication Facility

Cornell University, Ithaca, NY 14853-5403 USA

NEB-22, a chemically amplified negative tone resist has been formulated by Sumitomo for e-beam lithography
direct write and mask making applications. The resist has exhibited excellent characteristics which would also
make it applicable for use in a SCALPEL exposure tool. 1'2 The initial processing results for Sumitomo NEB-
22A5 material demonstrated extremely high resolution capabilities with excellent exposure latitude. Although the
process worked well for many direct write and mask applications, improvements were needed to address
SCALPEL concerns. The process was modified to maintain sensitivity and optimize resolution, exposure latitude
and PEB latitude. Excellent results were obtained in a 200 nm film of NEB-22 with new process parameters.

1. I N T R O D U C T I O N how process modifications could benefit direct write,

Modem electron beam lithography systems are
capable of generating sub 250 nm lines with a very
high level of pattern placement accuracy and control.
Lithography development roadmaps currently include
e-beam exposure systems as possible lithographic
manufacturing tools for the _<100 nm applications.
NEB-22, a chemically amplified negative tone resist
has been formulated by Sumitomo for e-beam
lithography direct write and mask making
applications. The resist has exhibited excellent
characteristics which would also make it applicable
for use in a SCALPEL exposure tool. 1'2
Space charge issues limit the exposure current in
a SCALPEL system 3. In order to maximize
throughput, a resist which exhibits both good
resolution and sensitivity is desirable. The initial
processing results for Sumitomo NEB-22A5 material
has shown extremely high resolution capabilities
with excellent exposure latitude for both isolated and
line/space features ~. Although the process works well
for many direct write and mask applications, the
resist needs to be optimized to address SCALPEL
concems. The purpose of this work was to understand
0167-9317/99/$- see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S0167-9317(99)00108-2
mask writing and SCALPEL applications.
2. EXPERIMENTAL DETAILS
The majority of the results for this work have been
obtained using a Leica EBML300 Electron Beam
exposure system using a beam voltage of 40 keV.
The patterns were exposed using a field size of
0.8192 mm (25 nm pixel size) for all of the process
development work. The beam current and spot size
were 200 pA and 80 nm, respectively. In order to
further understand the capabilities of the NEB-22
resist, selected samples were also exposed on a Leica
VB6 exposure system, operating at 100 keV. The
address grid, exposure current and beam size were 20
nm, 1.5 nA and 25 nm, respectively. All resist
processing was performed on silicon substrates with
hexamethyldisilizane (HMDS) treatment prior to
resist coat and all bakes were performed on a hotplate
in contact mode. Wafers were immersion developed
in TMAH based developers, rinsed in DI water and
spin dried. Linewidth measurements were performed
on an Amray 1860 FE SEM with WICS linewidth
analysis software.
376 E. Ainley et al. I Microelectronic Engineering 46 (1999) 375-378

3. RESULTS 3.2 Developer Normality

3.1 Initial Processing Conditions A common practice for improving resist

response is to use a less aggressive developer.
A 400 nm film was selected for the initial Previous work t* has demonstrated that lowering the
resolution tests. A prebake of 110° C for 120 normality of the developer for a negative chemically
seconds resulted in the desired film thickness. A amplified resist increases contrast and lowers the
resolution pattern with line/space gratings, isolated exposure dose. The pattern holds true for NEB-22.
lines and isolated via/post features down to 100 nm By decreasing the normality to 0.21N, the contrast
was exposed between 2 and 20 ~tC/cm 2. The post of the resist increases from 3.3 up to 5 (Figure 2).
exposure bake (PEB) temperature was 105 °C for 1.2 • , i ' ' ' i , , , i , , , i , , ' i ' ' ' i ' ' '
120 seconds. The recommended developer strength
and time was 0.26N TMAH and 40 seconds, c I y=5. ~,~ -~- "e--_ =
respectively. The dissolution rate of unexposed resist 32
was measured at 100 nm/sec, resulting in a 10X I- 0.8 = .
tm CD
overdevelopment. Wafers processed with the above • -= I- -M 02 I
conditions showed excellent resolution and latitude. •-~ 0.6
100 nm features were resolved at 12 ~tC/cm 2 with a E
or 0.4
13 nrn/~tC/cm 2 latitude (Figure 1). Resist contrast
for these conditions was 3.3. Additional tests also
confirmed little CD variation as a result of either
extending the time between prebake and exposure or
between exposure (while still under vacuum) and
- ! l
--~ 0.2
or
0
0
,4_ ~,..',~'.,,',,,',,,',,,
2 4 6 8 10 12 14
PEB 1. Exposure Dose (gC/cm2)
600 . . . . . . . . . , . . . . . . . . . , . . . . . . . . . Figure 2. Resist contrast for two developers.

5OO
E Using the 0.21N developer, a DOE was
e-
0
400 I 100°mI
•
150
250
nm
nm
constructed to optimize the prebake, PEB, and
developer time similar to the work done by Mancini
v 500 nm
m
.E
300 et al. 8 The 15 experiments comprising the Box-
E3 Behnken response surface design for this analysis
200

:Z'-
were laid out using JMP statistical software. The
(.5 100
prediction profile generated by JMP is depicted in

0 . . . . . . . . . i . . . . . . . . . t . . . . . i i i i

10 15 20

Dose (p.C/cm 2)

Figure 1. Critical dimension vs. exposure dose. 12

~tC/cm2 was required to resolve the 100 nm features.

In order to optimize throughput, the SCALPEL

technology requires a resist sensitivity of 10 ~tC/cm 2
at 100 keV 3. The 1997 SIA roadmap also
recommends that the PEB sensitivity be no greater
than 5 nm/°C. Under the processing conditions just
described, the PEB sensitivity was 14 nm/°C. In
order to improve sensitivity and latitude, four
process parameters were varied: developer normality,
PEB temperature and time, and prebake time. Figure 3. Prediction profile using a 0.21N developer.
 E. Ainley et al. / Microelectronic Engineering 46 (1999) 375-378 377

Figure 3. Operating dose, dose latitude and line
edge roughness were examined, varying prebake
temperature PEB temperature and developer time.
Operating dose is clearly reduced by using a lower
normality developer. Exposure latitude increased
significantly as a result of the lower operating dose.
It is interesting to note that line edge roughness
decreases by using shorter develop times. In a
separate experiment, it was also determined that the
PEB latitude was reduced to 10 nm/°C.
3.3 PEB Temperature and Time
~tC/cm 2, the 100 nm dense lines measured 97 nm.
The 500 nm dense lines measured 510 nm. It is
interesting to note that if resist sensitivity is not a
concern, excellent exposure latitude can be achieved
by lowering the PEB temperature to 90 °C.
Not depicted in Figure 4 is the effect of
temperature and time on resolution. Although it is
possible to achieve a sensitivity of less than 5
~tC/cm:, the higher temperature and weaker developer
degrade resolution. SEMs taken at 90 and 105 °C
demonstrate this effect (See Figure 5).

Previous work on NEB-22 has demonstrated that

increased PEB time can improve exposure latitude 2.
A systematic study was done to understand the effect
of both PEB time and temperature. A full factorial
experiment examined the effects on operating dose,
exposure latitude and PEB latitude. A JMP
prediction profile depicts the results of this study.

: :~!i!i~iiill::#

5a 5b

Figure 5. SEMs of 100 nm features, depicting the

i i loss of resolution at the higher PEB temperature.

i 3.4 Prebake Time

In order to see whether additional improvements

Ii Ii could be made, a brief study examined the effects of
increasing the prebake time. The results of one set of
conditions are shown in Figure 6. For this particular
run, prebake temperature and time were 110 °C and
240 seconds, respectively. PEB temperature and time
Figure 4. Prediction profile for NEB22, examining
600
the effects of varying PEB temperature and time.
. x . ~ _ ~._-----v
5OO f

There are several tradeoffs when choosing PEB E

|
400 • 100 nm I
temperature and time. A temperature of 95 °C was 4, 150 nm

I
O
• 250 nm
chosen in order realize reasonable resist sensitivity. c
•. 500 nm
300
At this condition, the exposure latitude is improved
121 "e @

by more than a factor of two over the operating -~ 200

point chosen from Figure 3. A PEB time of 240
seconds was selected, yielding improved PEB latitude 0 100

(7.7 nm/°C), without severely impacting exposure 0 . . . . i . . . . i . . . . i , , , 1 1 1 , , , i . . . . i . . . . i , . , I

latitude. If necessary, operating dose can be decreased 10 11 12 13 14 15 16 17 18

simply by increasing the PEB time to 300 seconds. Dose (gC/cm 2)
Feature size linearity was excellent using these Figure 6. Exposure latitude using a prebake
processing parameters. At an exposure dose of 12 temperature and time of 110 °C and 240 seconds.
378 E. Ainley et al. / Microelectronic Engineering 46 (1999) 375-378

were held at 95 °C and 240 seconds. Development

time using 0.21N MF702 was 40 seconds.
The prolonged prebake temperature causes an
increase in operating dose. Although a small
improvement in exposure latitude is realized, the
gain is tempered by a loss in resist sensitivity.
Feature size linearity is also comparable to the
results observed with shorter prebake times. In
addition, a separate experiment determined that no
further improvement in PEB latitude was achieved.

4. 100 k e V Results

In order to better understand resist performance

Figure 8. 30, 60, 100 and 250 nm images obtained
at 100 keV and to examine resist resolution, final
in NEB-22 resist using a 100 keV Leica VB6 tool.
exposures were done on a Leica VB6 system
operating at 100 keV. Also, to avoid any aspect ratio
5. CONCLUSIONS
issues for the smaller features, the resist was thinned
to 200 nm. The processing parameters used in this
Significant improvements have been made to the
experiment were as follows:
processing conditions used for Sumitomo's NEB-22
Prebake Temp: 110 °C Prebake Time: 120 sec resist. A lower normality developer, lower PEB
PEB Temp: 95 °C PEB Time: 240 sec temperature and longer PEB times improved
Developer: 0.21N Develop Time: 40 sec resolution, contrast, exposure latitude and PEB
latitude. While the resist can benefit many direct
write and mask programs, further improvements to
A test pattern consisting of both dense and the resist are necessary to meet the stringent
isolated lines with features as small as 10 nm was requirements for the SCALPEL technology.
used as a test vehicle. The exposure latitude was
excellent. The results are shown in Figure 7. As ACKNOWLEDGMENTS
depicted in Figure 8, dense features as small as 60
nm and isolated features down to 30 nm are clearly The authors gratefully acknowledge Adolpho Rios for
resolved. At 40 keV the best resolution was 80 nm. e-beam exposure, and Toby Parker and Theresa
Hopson for SEM work. Finally, the authors would
6O0 1 i i i i like to acknowledge Laura Siragusa for supporting
500 nm this effort. This work was performed in part at the
E 500 • • • • 250 nm
t- • 150 nm National Nanofabrica.tion Facility, which is
t- ~ 100 nm
.O 400 80 nrn supported by the NSF under Grant No. ECS931005,
(/} •", 60 nm
¢- Cornell University and Industrial Affiliates.
E 300
• ~ A • • REFERENCES
"~ 200
¢..)
1. E. Ainley, presented at the 42nd EIPBN
(.~ 100
International Symposium, 1998.
A A A
0 . . . . I . . . . I . . . . I . . . . L . . . . I . . . .
2. L. E. Ocola, presented at the 42nd EIPBN
45 50 55 60 65 70 75 International Symposium, 1998
Exposure Dose (gC/cm 2) 3. L. R. Harriot, J. Vac. Sci. Technol. B 15, (1997).
4. K. Nordquist, J. Vac. Sci. Technol. B 15, (1997).
Figure 7. Critical dimension vs. exposure dose for 5. D. P. Mancini, Proceedings SPIE Vol. 2723,
200 nm NEB22, exposed at 100 keV. (1996).