Top-Surface Imaged Resists For 193-nm Lithography

Chapter 18
Top-Surface Imaged Resists for 193-nm

Lithography
Roderick R. Kunz, Susan C. Palmateer, Mark W. Horn,

Anthony R. Forte, and Mordechai Rothschild
Lincoln Laboratory, Massachusetts Institute of Technology,

Lexington, MA 02173-9108
Downloaded by UNIV OF LIVERPOOL on May 14, 2018 | https://pubs.acs.org
Publication Date: May 5, 1995 | doi: 10.1021/bk-1995-0614.ch018
We have optimized a positive-tone silylation process using

polyvinylphenol resist and dimethylsilyldimethylamine as the
silylating agent. Imaging quality and process latitude have been
evaluated at 193 nm using a 0.5-NA SVGL prototype exposure
system. A low-temperature dry etch process was developed that
produces vertical resist profiles resulting in large exposure and
defocus latitudes, linearity of gratings down to 0.175 μm, and
resolution of0.15-μmgratings and isolated lines.
Optical lithography using 193-nm radiation (ArF excimer laser) is a leading

candidate for mandfacturing integrated circuits with sub-0.25-pm features, such as
the 1-Gb DRAM. For this technology to be realized photoresists sensitive to 193-
nm radiation must be developed. At longer wavelengths, single-layer bulk
photoresists have been and continue to be the dominant technology, largely because
of their proven track record and mature commercial infrastructure. However, the
single-layer bulk approach has become more complex and expensive as the
exposure wavelength decreases to 248 and 193 nm. This trend sternsfromthe need
for acid-catalyzed resist chemistries and for antireflective coatings. Furthermore, at
the shorter exposure wavelengths the thickness of the resist approaches the total
focal plane depth of the exposure optics, thereby reducing the process depth of
focus to values which are unpractically small in a manufacturing environment.
Top-surface imaged (TSI) resists have been developed as an alternative to bulk
imaged resists (1). These TSI resist processes operate via area-selective in-
diffusion of a silyl amine into a phenolic polymer to form a silyl ether. Once the
silicon has been selectively incorporated, the latent image is developed in an
anisotropic oxygen plasma etch. At 193 nm, the simplest TSI resist scheme is
based on photocrosslinking of the polymer, followed by selective silylation of the
unexposed areas (2). Although chemical amplification schemes offer higher
sensitivity (3) and may ultimately be the process of choice, the single-component
direct crosslinking approach provides a simple platform for initial process
evaluation of TSI at 193 nm. In this paper we report on recent lithographic results
obtained by imaging with a prototype large-field step-and-scan exposure system,
which is operational in Lincoln Laboratory's class 10 cleanroom.
0097-6156/95^)614-0271$12.00A)
© 1995 American Chemical Society
Reichmanis et al.; Microelectronics Technology

ACS Symposium Series; American Chemical Society: Washington, DC, 1995.
272 MICROELECTRONICS TECHNOLOGY
193-nm
m u; w u; m
CROSSLINKED
PATTERNED POLYVINYLPHENOL
"Mr RESIST
EXPOSURE SPIN-ON RESIST
^ζζΔ
/ / /
SUBSTRATE
τ
SILYLATED
RESIST
SILYLATION
g^sio 2
OXYGEN
PLASMA
DEVELOPMENT
Figure 1 Schematic processflowfor 193-nm silylation.
294 292 290 288 286 284 282 280
B
N
IDN
IG ENERGY (eV)
Figure 2 Carbon Is x-ray photoelectron spectra for PVP irradiated at 193-nm
in air for the indicated doses.

18. KUNZ ET AL. Top-Surface Imaged Resists for 193-nm Lithography 273
Experimental
The positive-tone 193-nm silylation resist process is illustrated schematically in
Figure 1. A polyvinylphenol (PVP) resin of molecular weight M of 38,000 g/mol
w
is selectively crosslinked by exposure on a 0.5-NA step-and-scan 193-nm optical

lithography system. The sample is then treated with a silicon-containing vapor,
dimethylsilyldimethylamine (DMSDMA), at a temperature of 90°C and a pressure of
25 Torr for 30 to 75 s. The uncrosslinked PVP areas incorporate a controlled
amount of silicon, whereas the crosslinked areas exhibit near-zero silicon
incorporation. The wafers are then dry developed in a high-ion-density helicon
plasma etcher in an oxygen-based plasma (4,5). The oxygen reacts with the
silylated areas to form S1O2, which acts as an etch mask in the unexposed areas.
The silylation resist process has been evaluated as two separate steps, the silylating
agent diffusion/reaction and the oxygen plasma etching. We have performed
scanning electron microscope (SEM) metrology of the silylated profiles, including

exposure-defocus matrices for the silylation step alone. This approach treats the
silylation as a step which can be optimized independently from aie exposure and
etching.
In parallel, the etching step has been studied and optimized with respect to resist
profile, etch rate, uniformity across the wafer, and selectivity between exposed and
unexposed areas. First, unpatterned wafers consisting of a 0.50- to 0.76-pm-thick
PVP film with a 100-nm-thick silylated layer were used to optimize the rf source
power, chuck power, O2 flow rate, temperature and pressure. An imaging
interferometry system was used for these measurements, resulting in greatly
reduced process development times (6). Then, patterned trilayers consisting of a
Ι.Ι-μπι-thick hard-baked resist planarizing layer, a 0.2^m-thick S1O2 hardmask,
and a 0.3^m-thick resist imaging layer were used to optimize the resist profile
independently of the silylation mask shape. Finally, patterned silylation wafers
were etched to evaluate pattern transfer into resist and process latitudes for the
silylation process. Lithographic results were all obtained by performing SEM
measurements. An Amray SEM equipped with a WICS measurement system for
top-down critical dimension (CD) measurements was used.
Results and Discussion
Resist and Silylating Agent Chemistry. Characteristics of 193-nm-based
TSI resist processes differ from those at other wavelengths. For example, neat
1
PVP used in these studies has an absorption coefficient α of roughly 25 μ π τ at
1
193 nm, limiting the crosslinking to the top -50 nm, in contrast with α -0.5 μ π τ
at 248 nm. In addition, direct photochemical crosslinking at levels sufficient to
2
inhibit silylation occurs at 193 nm for exposure doses of only 50 mJ/cm , whereas
2
doses in excess of 500 mJ/cm are necessary at 248 nm. As a result, efficient
crosslinking at 248 nm can be accomplished only through addition of sensitizers
and crosslinkers, and true TSI is only achieved through addition of a dye (7).
2
These factors are important at 193 nm only when high photospeed (<20 mJ/cm ) is
desired. For unsensitized PVP, we believe the crosslinking mechanism to proceed
via free-radical intermediates analogous to those present during UV-induced
crosslinking of polystyrene (8). Little or no contribution to crosslinking is achieved
through oxidative mechanisms involving quinone derivatives, as indicated by the
2
carbon Is XPS spectra of PVP irradiated at doses of 50, 500, and 2000 mJ/cm ,
shown in Figure 2.

Based on initial materials characterization we chose to use DMSDMA to silylate the

PVP because of its high vapor pressure and small molar volume, which allows it to
diffuse rapidly at low temperatures. This is useful for our single-component high-
molecular-weight PVP resist which has a higher glass transition temperature (Tg),
~180°C., than many multiple-component chemically amplified TSI resists. One
effect of this high Tg is slower diffusion rates which can be minimized by going to
lower-molar-volume silylating agents. The larger-molecular-weight analogs
trimethyMyldimethylamine (TMSDMA) and trimethylsUyldiethylamine (TMSDEA)
were also used to silylate PVP (9,10). The absolute diffusion/reaction rate is
significantly faster for the smaller-molecule DMSDMA, while the silylation contrast
for all three reagents are comparable. Because of these considerations we have
optimized our process with DMSDMA, and the results reported below have been
obtained with this silylating agent.

Silylation Mask Shape. For a positive-tone process, the silylation mask shape
is governed by the silylating diffusion agent through the crosslinked latent image in
the exposed resist film. For PVP and DMSDMA the diffusion process and its
dependence on feature size and type have been studied in detail previously (11).
Figure 3 shows SEM images of plasma-stained samples of the silylation mask
shape for 0.25-μτη gratings as a function of exposure energy and defocus, when
the open field silylation is 200 nm deep. Note the relatively weak dependence of
the silylated profile linewidth on defocus, i.e., only at the extremes of defocus
(greater than ±0.8 μπι) does the profile linewidth change dramatically. However,
the profile angle, which is critical in determining how much dimensional loss
occurs during the dry development step (12), does become somewhat narrower at
modest (±0.5 μπι) defocus (13). Not only does this behavior place greater
demands on the dry development step to realize the maximum depth of focus, but
we have found the profile angle to be profoundly affected by silylation conditions
as well. As such, well-optimized dry development conditions are essential in
realizing the maximum process window for a given set of silylation conditions.
MOSES (Modeling of Surface Exposed Systems), an empirical model developed at
Lincoln Laboratory, has been used to simulate silylation mask shape and its
response to both defocus and the dry development conditions, to predict linewidth
control and process latitude (13). Results of the simulations, together with the
experimentally measured profiles, have been used to qualitatively optimize the
silylation process latitude.
Dry Development. The following trends have been observed in the 02-plasma
etching of PVP, using the helicon etcher. The etch rate increases with increasing
source powerfrom-0.95 μιη/min at 1 kW to 1.4 μπι/min at 2.5 kW. The etch rate
increases with chuck powerfrom1.1 μπι/min at 20 W to 1.7 μπι/min at 90 W. The
etch rate also increases with flow rate (from 0.85 μτη/πύη at 25 seem to 1.3 μπι/min
at 100 seem). The etch rate increases from 1.4 to 1.6 μπι/min when the wafer
temperature is reducedfrom30 to -70°C. This is consistent with etchants adsorbing
to the resist: adsorption of reactive species increases at lower temperatures and
enhances the ion-assisted etching rate (14,15). The etch rate is nearly independent
of pressure between 1 and 6 mTorr. To achieve lower pressures the flow rate had
to be decreased to 50 seem, and these experiments indicated that from 1 to 0.5
mTorr the etch rate decreasesfrom1.05 to 0.90 μπι/min. Our results also indicate
that the etch rate varies with the amount of material being removed, consistent with
results reported by Jurgensen et al (16). Under identical plasma conditions, the
etch rate decreases with increasing wafer size,from1.65 μπι/min for 3-in.-diameter
wafers, to 1.35 μπι/min for 4-in.-diameter wafers, to 1.05 μπι/min for 6-in.-
diameter wafers. The dependence of etch rate on flow rate and wafer size indicates
that loading effects are important in this helicon etcher.

Selectivity between the silylated and unsilylated resist is the variable which most
dramatically affects exposure, focus and etch process latitude as well as feature
linearity. We have found that the chuck power is the etching parameter that
produces the largest change in selectivity,from-160:1 at 20 W to less than 20:1 at
90 W. Selectivity is nearly independent of pressure (2 to 6 mTorr) and wafer
temperature (30 to -70°C) at 2-kW source power, 50- to 75-W chuck power and
100-sccm O2. Again we note a change at low pressure where the selectivity
decreases from 30:1 at 2 mTorr to 20:1 at 0.5 mTorr, all other variables remaining
the same. The selectivity at a given chuck power can be increased by increasing the
flow rate or the source power. To obtain acceptable linewidth control with the 193-
nm silylation resist, MOSES modeling indicates that a selectivity greater than 20:1
is required. This requirement can be satisfied by lowering the chuck power.
However, a lower limit on chuck power is imposed by the need to maintain a low
lateral etch rate, for profile control (see below). Thus, an operating window on the
chuck power is defined. For typical conditions of 2-kW source power, 2-mTorr
pressure, 100-sccm O2, and -70°C., it is 35 to 75 W. Under these optimized

process conditions blanket wafer etch rate nonuniformity is less than ±3% over the
central 85 mm of a 100-mm wafer.
In addition to adequate selectivity, it is necessary to optimize the resist profile. We
used patterned trilayers with a S1O2 hardmask to evaluate the effect of etch process
parameters on resist profile under idealized silylation mask shape. A high degree of
anisotropy is obtained by increasing the chuck power and decreasing the wafer
temperature (14,15). Decreasing the wafer temperaturefrom30 to -70°C practically
eliminates the isotropic etch component, while the vertical etch rate increases by
about 15% (Figure 4). An alternative way to reduce the lateral etch rate is to use a
sidewall passivating gas such as SO2. However, the lateral etch rate is not
eliminated but only reduced to -20 nm/min, a value which causes a greater than
10% variation in 0.18-μτη linewidths (17).
Lithographic Results. The overall lithographic performance of the silylation
process depends on both the silylation step (i.e., the silylation mask shape) and the
dry development step (i.e., selectivity, vertical/lateral etch rates and amount of
overetch). One of the main criteria for good performance is linearity, i.e., the
ability to print a wide range of feature sizes and types within prescribed tolerances
(e.g., ±10% of linewidth). Figure 5 demonstrates the excellent linearity obtained
with 193-nm TSI, using the process conditions listed in Table I for a 100%
overetch and a 60-s silylation time (open field silylation depth 200 nm). For a
wafer temperature of -70°C., linearity is maintained down to 0.20 μπι for both a 25
and 100% overetch. For an etch temperature of 30°C., linearity is maintained down
to 0.20 μπι for a 25% overetch, but only to 0.30 μπι for a 100% overetch. This is
due to an increased isotropic etching component at 30°C. The nominal best dose for
a 100% overetch is 20% lower than for a 25% overetch in order to enable more
silylation which compensates for the linewidth erosion occurring during longer
etch.
The preceding linearity data are for a fixed silylation time (60 s). Dense feature
linearity was extended down to 0.175 μπι for a 30-s silylation time using the
process conditions in Table I and a 25% overetch. For longer silylation times (60
to 75 s) feature linearity could not be maintained below 0.25-μτη features for these
process conditions.

Figure 3 Scanning electron micrographs showing the variation in the profile of

silylated areas with changes in exposure dose and defocus. The features were
nominally 0.25-μτη equal lines and spaces. Each 193-nm dose unit corresponds
2
to -1 mJ/cm . Silylation was performed with 25-Torr DMSDMA at 90°C for
60 s.
.75 -50 -25 0 25 50 75 100

WAFER TEMPERATURE (°C)
Figure 4 Vertical and lateral resist etch rates vs actual wafer temperature
measured for 0.70-pm-wide isolated lines patterned in trilayers.

Table I Silylation Process Parameters

Parameter Conditions
Substrate HMDS-treated Si (100) 100-mm-diameter
wafers
Resist 0.50-to0.76^mPVP
Post-apply bake 120°C.,60s
Exposure SVGL 193-nm step and scan 0.5 NA

Silylation DMSDMA 90°C/25 Torr/30-75 s
Dry development 2-kW source power, 75-W chuck power,

2-mTorr pressure, 100-sccm 02, -70°C.,
helicon etcher
Resist etch rate 1.6 μπι/min
Selectivity 27:1 open field
MASK CD (μηι)
FigureS Silylation process linearity at best dose (100 dose units -100
2
mJ/cm ). Resist 0.76^m-thick PVP silylated with DMSDMA at 90°C and 25
Torr for 60 s was etched under optimized conditions (see Table I) with a 100%
overetch. The grating linearity is extended to 0.175 μπι for a 30-s silylation time
and 25% overetch. The two solid lines are the acceptable performance, i.e.,
±10% deviationsfromthe nominal feature size.

In addition to linearity, lithographic performance is also judged by the extent of the

exposure and defocus process latitudes. Figure 6 is a graphic representation of the
exposure-dose matrix for 0.20-, 0.175- and 0.15-μπι gratings for a 30-s silylation
time and a 25% overetch. At best dose the depth of focus is 1.6,1.0, and 1.0 μπι,
respectively. However, this maximum depth of focus is obtained at higher doses as
the feature size decreases. Such behavior is in qualitative agreement with the aerial
image and corresponding exposure-defocus plots (18). Figure 7 shows SEMs of
0.20-μπι silylated resist features, whereas Figure 8 shows 0.15-μπι isolated and
dense features.
Figure 6 Experimental exposure-dose matrix for 0.20-, 0.175-, and 0.15-μπι

2
gratings, (±10% CD). Each 193-nm dose unit corresponds to ~1 mJ/cm .
Resist 0.50-pm-thick PVP silylated with DMSDMA at 90°C and 25 Torr for 30 s
was etched under optimized conditions (see Table I) with a 25% overetch.
Conclusions
The large process latitudes, linearity, depth of focus, and exposure latitude obtained
using silylation at 193 nm make it an extremely attractive process for 8υ^0.25-μτη
lithography. By understanding both the silylation and dry development steps and
their interplay, the process can be further optimized for different feature sizes and
types. Other concerns regarding implementation of TSI in manufacturing are
related to its perceived higher cost than that of single-layer resist. Although outside
the scope of this paper, it is worth noting that a simple cost of ownership
calculation demonstrates that the TSI approach is competitive with the single-layer
approach (assuming the yields are equivalent) and that cost should not be the
deterring factor in implementing TSI for 248-nm imaging (19).

18. KUNZ ET AL. Top-Surface Imaged Resists for 193-nm Lithography
279
Figure 7 Scanning electron micrograph of 0.20-μτη silylated resist features.

Resist 0.76-jim-thick PVP silylated with DMSDMA at 90°C and 25 Torr for 60 s
was etched under optimized conditions (see Table I) with a 100% overetch.
Figure 8 Scanning electron micrograph of 0.15-μτη (a) isolated and (b) dense
features. The doses used for these two features were not the same.
Acknowledgments
We would like to acknowledge the help of Lynn Eriksen on silylation, Scott Doran
for aerial image simulations, and Cheryl Graves for SEM work. This work was
supported by the Advanced Lithography Program of the Advanced Research
Projects Agency. Opinions, interpretations, conclusions, and recommendations are
those of the author and are not necessarily endorsed by the United States Air Force.

Literature Cited
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Electrochem. Soc. 131, 1664 (1984).
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Shaver, J. Vac. Sci. Technol. Β 8, 1476 (1990).
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4. Benjamin, N . ; Chapman, B.; and Boswell, R., SPIE Proc. 1392, 95
(1990).
5. Horn, M . W.; Hartney, Μ. Α.; and Kunz, R. R., SPIE Proc. 1672, 448
(1992).
6. Low Entropy Systems, Inc., 83A Monroe Street, Somerville, MA 02143.

7. Linehan, L.; Conley, W.; Stewart, K.; Wood, R.; Muller, K. P.; and
LaTulipe, D., in Extended Abstracts, 10th International Symposium of the Society

of Plastics Engineers, Inc., Mid-Hudson Section, Ellenville, NY, October 31 - 2
November 1994.
8. Ranby, B. and Rabek, J. F., in Photodegradation Photo-oxidation and
Photostabilization of Polymers: Principles and Applications, Wiley-Interscience,
New York, 1975.
9. Hartney, Μ. Α.; Johnson; D. W.; and Spencer, A. C., SPIE Proc. 1466,
238 (1991).
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(1991).
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hove, L, SPIE Proc. 2195, 394 (1994).
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464 (1993).
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(1994).
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Chapter 18

Top-Surface Imaged Resists for 193-nm

Roderick R. Kunz, Susan C. Palmateer, Mark W. Horn,

Lincoln Laboratory, Massachusetts Institute of Technology,

We have optimized a positive-tone silylation process using

Optical lithography using 193-nm radiation (ArF excimer laser) is a leading

Reichmanis et al.; Microelectronics Technology

Figure 1 Schematic processflowfor 193-nm silylation.

294 292 290 288 286 284 282 280

Reichmanis et al.; Microelectronics Technology

is selectively crosslinked by exposure on a 0.5-NA step-and-scan 193-nm optical

scanning electron microscope (SEM) metrology of the silylated profiles, including

Reichmanis et al.; Microelectronics Technology

Based on initial materials characterization we chose to use DMSDMA to silylate the

obtained with this silylating agent.

Reichmanis et al.; Microelectronics Technology

pressure, 100-sccm O2, and -70°C., it is 35 to 75 W. Under these optimized

Reichmanis et al.; Microelectronics Technology

Figure 3 Scanning electron micrographs showing the variation in the profile of

.75 -50 -25 0 25 50 75 100

Reichmanis et al.; Microelectronics Technology

Table I Silylation Process Parameters

Exposure SVGL 193-nm step and scan 0.5 NA

Dry development 2-kW source power, 75-W chuck power,

Reichmanis et al.; Microelectronics Technology

In addition to linearity, lithographic performance is also judged by the extent of the

Figure 6 Experimental exposure-dose matrix for 0.20-, 0.175-, and 0.15-μπι

Reichmanis et al.; Microelectronics Technology

Figure 7 Scanning electron micrograph of 0.20-μτη silylated resist features.

Reichmanis et al.; Microelectronics Technology

6. Low Entropy Systems, Inc., 83A Monroe Street, Somerville, MA 02143.

LaTulipe, D., in Extended Abstracts, 10th International Symposium of the Society

Reichmanis et al.; Microelectronics Technology

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