Real-time studies of surface roughness development and reticulation mechanism of

advanced photoresist materials during plasma processing

A. R. Pal, R. L. Bruce, F. Weilnboeck, S. Engelmann, T. Lin, M.-S. Kuo, R. Phaneuf, and G. S. Oehrlein

Citation: Journal of Applied Physics 105, 013311 (2009); doi: 10.1063/1.3055268

View online: http://dx.doi.org/10.1063/1.3055268
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/105/1?ver=pdfcov
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 JOURNAL OF APPLIED PHYSICS 105, 013311 共2009兲

Real-time studies of surface roughness development and reticulation

mechanism of advanced photoresist materials during plasma processing
A. R. Pal,1,2,a兲 R. L. Bruce,1,2 F. Weilnboeck,1,2 S. Engelmann,1,2 T. Lin,1,3 M.-S. Kuo,1,2
R. Phaneuf,1,3 and G. S. Oehrlein1,2
1
Department of Materials Science and Engineering, University of Maryland, College Park,
Maryland 20742, USA
2
Institute for Research in Electronics and Applied Physics, University of Maryland, College Park,
Maryland 20742, USA
3
Laboratory for Physical Sciences, University of Maryland, College Park, Maryland 20742, USA
共Received 30 August 2008; accepted 14 November 2008; published online 12 January 2009兲
Surface roughness development of photoresist 共PR兲 films during low pressure plasma etching has
been studied using real-time laser light scattering from photoresist materials along with
ellipsometric and atomic force microscopy 共AFM兲 characterization. We show that evolution of the
intensity of light scattered from a film surface can be used to study the development of surface
roughness for a wide range of roughness starting from subnanometer to few hundred nanometers.
Laser light scattering in combination with ellipsometry and AFM is also used to study the
reticulation mechanism of 193 and 248 nm PRs during argon plasma processing. We employ a
three-layer model 共modified layer, rough layer, and bulk film兲 of the modified PR surface 共193 and
248 nm PRs兲 to simulate and understand the behavior of ellipsometric ⌿-⌬ trajectories.
Bruggeman’s effective medium approximation is employed to study the roughness that develops on
the surface after reticulation. When the glass transition temperature of the organic materials is
reached during Ar plasma processing, the PR films reticulate and roughness develops rapidly.
Roughness development is more pronounced for 248 nm PR than for 193 nm PR. Simulation of
⌿-⌬ shows that the growth of roughness is accompanied by strong expansion in the materials,
which is stronger for 248 nm PR than 193 nm PR. The leading factors responsible for reticulation
are found to be compressive stress that develops in the modified surface layer as it is created along
with strong molecular chain motion and expansion of the material when the temperature is increased
past the glass transition temperature. Reticulation leads to a significantly different surface
morphology for 248 nm PR as compared to 193 nm PR and can be related to differences in
molecular structure and composition leading to different responses when a modified surface layer is
formed by ion bombardment accompanying plasma etching. © 2009 American Institute of Physics.
关DOI: 10.1063/1.3055268兴

I. INTRODUCTION
Photoresists 共PRs兲 are widely used as a masking material
in the process of plasma-based pattern transfer in nanoscale
dimensions.1–3 A vital concern is the development of surface
and line-edge roughnesses during the transfer of patterns
from PR to the underlying material during the plasma
process.4–6 To develop plasma processing conditions that
minimize surface roughness, real-time monitoring of surface
roughness is useful.
Distinct from surface roughness formation at low sub-
strate temperature is photoresist reticulation, where the PR
surface degrades and strong roughness develops when the
temperature of the material reaches its glass transition
temperature.7–9 The reticulation process has been used to
measure the wafer temperature using the reticulation thresh-
old temperature.7 Reticulation must be prevented during
plasma etching.8,9 An important factor controlling reticula-
tion is the temperature rise of the thin film material, which
a兲
Permanent address: Material Sciences Division, Institute of Advanced
Study in Science and Technology, Paschim Boragaon, Garchuk, Guwahati-
781035, India. Electronic addresses: arup_trip@yahoo.com and
aruprp1@gmail.com.
depends on the power deposition into the film and can be
controlled by plasma density and wafer bias voltage.
Atomic force microscopy 共AFM兲 is commonly used to
measure surface roughness of plasma treated films, but this
technique cannot be used for real-time measurements. On the
other hand, surface roughness evolution can be performed in
real-time during the plasma process using light scattering.
For instance, light scattering by small particles in discharges
has been studied for many applications. The governing theo-
ries are Mie’s theory for scattering by small particles and
Rayleigh scattering for the situation when the size of the
scatterer is smaller than the wavelength of light.10 Rayleigh–
Rice vector perturbation theory is particularly useful for the
study of light scattering by a rough surface where the scale
of the roughness is much smaller than the wavelength of
light used for the measurement.11,12 Scattered light intensity
共I兲 is proportional to the square of the roughness 共z兲, i.e.,
I⬁z2, while scattering also depends on other factors such as
the refractive index and the roughness correlation length.
Even if the latter factors vary during a process, surface
roughness will still dominate light scattering. Techniques
such as total integrated scattering are also useful for study of
roughness but are difficult to implement for real-time

0021-8979/2009/105共1兲/013311/9/$23.00 105, 013311-1 © 2009 American Institute of Physics

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 013311-2 Pal et al.
measurements.13 Some effects such as the interference be-
tween the light scattered from the substrate and from the
surface of the films may affect the accuracy of the results
when scattered light is used for roughness study.14,15 These
factors are not significant when the substrate roughness is
low, as is the case for silicon substrates covered by photore-
sist film.
In the present work, we have studied light scattering
from photoresist films in real-time during plasma etching of
photoresist on silicon substrates using an inductively coupled
plasma system equipped with a He–Ne laser and an optical
spectrometer. Our motivation is to implement this simple
technique for real-time studies of the growth of surface
roughness, even for situations for which the roughness scale
is very small. However, to illustrate the usefulness of the
technique, emphasis has been placed on studying light scat-
tering in combination with single wavelength in situ ellip-
sometry and AFM to study photoresist reticulation for differ-
ent plasma conditions.
II. EXPERIMENTAL
A. Materials
The materials used in this experiment are 193 nm PR,
248 nm PR, and a modified compound of 193 nm PR.6 These
materials are supplied by Rohm and Haas Electronics Mate-
rials. The reference compound, which serves as the basis of
the 193 nm PR and the modified compound, consists of a
methyl adamantyl methacrylate 共MAMA兲 in the leaving
group, an ␣-gamma butyrolactone methacrylate in the lac-
tone group 共␣-GBLMA兲, and an R-functionalized adamantyl
methacrylate in the polar group. This polymer structure is
typical of common 193 nm PR materials and is referred to as
MAMA. The modified compound is RADA for which the
methacrylate group is replaced by an acrylate in the polar
group. The details about the materials and the modified
forms are given in a recent publication from our group.6 The
material for which the sidegroup is largely composed of aro-
matic rings 共248 nm PR兲 is more etch resistant and develops
less surface roughness during plasma etching than the mate-
rials for which the sidegroup is methacrylate based 共193 nm
PR兲.6 The RADA material shows small but definite differ-
ence in roughening behavior from 193 nm PR and were stud-
ied to demonstrate the applicability of light scattering in dis-
tinguishing different ranges of surface roughness. Also, for a
comparison of reticulation behavior, the methacrylate based
共193 nm PR兲 and aromatic ring based 共248 nm PR兲 polymers
were selected.
B. Plasma processing and diagnostics
The inductively coupled plasma reactor used in this
work has been described in earlier articles of this group.16
The schematic diagram of the plasma system is presented in
Fig. 1. A planar coil is placed on top of a quartz window and
powered through an L-type matching network at a frequency
of 13.56 MHz with a power supply 0–1000 W. The ion en-
ergy at the wafer can be controlled independent of the
plasma generation by a variable frequency 0.4–40 MHz rf
power supply 0–300 W. For this study the rf frequency is
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J. Appl. Phys. 105, 013311 共2009兲
FIG. 1. Schematic diagram of the experimental setup.
fixed at 3.4 MHz and the self-bias voltage of the wafer is
varied up to ⫺100 V. The temperature of the electrode is
fixed at 10 ° C using backside substrate cooling. The total
gas flow rate is maintained at 40 SCCM 共where SCCM de-
notes standard cubic centimeter per minute at STP兲. An op-
erating pressure of 10–12 mTorr is achieved through control-
ling a throttle valve in the pumping line. Before each
experiment, the chamber was seasoned for 2 min applying
the conditions for the next experiment. Most of the experi-
ments described here were carried out in discharges operated
at a pressure of 10 mTorr at a flow rate of 40 SCCM and
maintained using 400 W source power.
To study the variation in scattered laser intensity with
roughness, we prepared samples in a similar reactor using
plasma conditions of 1000 W source power, ⫺100 V self
bias of the substrate, 10 mTorr pressure using a gas flow of
50 SCCM of 90% Ar/ C4F8, and employing a shutter ap-
proach in the gradient exposure mode described
previously.17–19
An optical spectrometer with charged-coupled device
detector was used for recording the light scattered from the
sample. The scattered light from the sample was detected at
a direction perpendicular to the plane of incidence making an
angle of about 70° with the surface normal 共see Fig. 1兲. This
direction is chosen so that contributions of scattering from
sample edges and also effects of reflection and interference
can be avoided. A rotating compensator ellipsometer in the
polarizer-compensator-sample-analyzer configuration with a
632.8 nm He–Ne laser was used to record the ellipsometric
⌿-⌬ and hence to study the modifications in the thickness
and optical constants in real time.
AFM measurements were performed on gradient ex-
posed, homogeneously plasma etched, and reticulated
samples. The scan size for all measurements was fixed at
10⫻ 10 ␮m2. The surface roughness values reported were
calculated from the root mean square 共rms兲 of the surface
profile after the measurement.
III. RESULTS AND DISCUSSION
To investigate whether light scattering can be utilized to
estimate the polymer film surface roughness when the mate-
rial reticulates and strong roughness develops, the scattered
 013311-3 Pal et al. J. Appl. Phys. 105, 013311 共2009兲

2
P (W/cm ):
12

(A.U.)
1.007
0.504
10 0.435
1/2

8
(Scattered Intensity)

TMax 248 nm
6

4
193 nm
2 T
R

0
0 20 40 60 80
Plasma Exposure Time (s)
FIG. 2. 共Color online兲 Variation in square root of the scattered intensity with
plasma exposure time for 248 nm and 193 nm PRs recorded in real-time
without sample cooling and observation of reticulation.

light is recorded in real time during argon plasma exposure

of 193 nm and 248 nm PR and the mechanism of reticulation
of PR is studied. The results are presented in Sec. III A. After
this experiment the applicability of light scattering for the
evaluation of small-scale roughness of PR samples is exam-
ined. For this, initially samples of 193 nm PR and RADA
were treated in Ar/ C4F8 plasma in gradient exposure mode
and the scattered light was measured in an external set up.
The results of this study are presented in Sec. III B. After
this, real-time measurements for similar plasma treatments
were performed. The result of the real-time measurement on
the small-scale roughness is presented in Sec. III C.

A. Real-time light scattering study of photoresist FIG. 3. 共Color online兲 AFM image of PRs showing large-scale roughness
reticulation formed due to reticulation: 共a兲 248 nm and 共b兲 193 nm.

1. Growth of roughness and variation of scattered

intensity with plasma exposure time
To study PR material reticulation, samples were etched
for 90 s in argon plasma at a source power of 400 W, a bias
voltage of ⫺50 to ⫺100 V, and pressure of 10–12 mTorr at a
flow rate of 40 SCCM. We have used three different combi-
nations of substrate bias and gas pressure to obtain different
power deposition rates to the wafer. These are: 共i兲 12 mTorr
and ⫺100 V 共power density at the wafer of 1.007 W / cm2兲,
共ii兲 12 mTorr and ⫺50 V 共power density at the wafer:
0.504 W / cm2兲, and 共iii兲 10 mTorr and ⫺50 V 共power den-
sity at the wafer of 0.435 W / cm2兲. To allow the samples to
heat up due to ion bombardment from the plasma, they were
kept thermally floating. The scattered light is recorded in
real-time and the ellipsometric ⌿-⌬ trajectory is recorded
simultaneously. As shown in Fig. 2 after few seconds of ex-
posure the scattered light intensity suddenly rises very rap-
idly and after peaking, decreases. For long exposure times,
there are indications of a slow increase. 248 nm PR shows
slightly higher exposure time required to reticulate as com-
pared to the 193 nm PR, although it has a lower glass tran-
sition temperature. Also the intensity after reticulation is
much higher for 248 nm PR than 193 nm PR.
Figure 3 shows AFM images of the 248 and 193 nm PRs
after reticulation for samples treated in argon plasma at a
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substrate power density of 0.435 W / cm2. To observe the
maximum roughness that develops after reticulation, plasma
is turned off when the scattered light intensity is at the peak
value 共see Fig. 2兲. For 248 nm PR the time required for
intensity to be maximum is 41 s and for 193 nm PR the
required time is 32 s. When turning off the plasma after the
scattered intensity reaches a maximum value, the intensity
does not decrease as is seen if the plasma process is contin-
ued. Instead, the scattered intensity actually increases after
the plasma has been turned off. This increase in the scattered
intensity after turning off the plasma appears to be due to
cooling of the PR material, contraction, and simultaneous
increase in surface roughness. From the AFM study we find
that the rms roughness value for 248 nm PR is 206 nm while
it is 85 nm for 193 nm PR. This observation is closely cor-
related with the intensity variation in the scattered light ac-
cording to the relationship 冑I ⬀ z where I is the scattered
laser intensity and z is the rms roughness. According to
Rayleigh–Rice vector theory the relationship 冑I ⬀ z holds for
polarized light scattered from a rough surface where the
scale of the roughness is much less than the wavelength of
light.11,12 This relationship also holds for unpolarized light
scattered from a rough surface where the roughness scale is
lower than the wavelength of light.13 There is a distinct dif-
 013311-4 Pal et al. J. Appl. Phys. 105, 013311 共2009兲

350

300
TMax

248 nm
T ( C) 250

193 nm
0

200

150
TR
100
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
2
P (W/cm )
FIG. 4. Temperature of the sample at reticulation 共TR兲 and temperature at
the time when scattered intensity is maximum 共Tmax兲 for 248 nm and 193
nm PRs.

ference in surface morphology of the two films after reticu-

lation 共see Fig. 3兲. Whereas the 248 nm PR forms a wavy
regular pattern, the 193 nm PR shows smaller feature sizes. It
seems that in case of 248 nm the surface layer remains but is
wrinkled, while in the case of 193 nm PR a mixed layer
comprising bulk material and surface layer forms on the sur-
face after reticulation. These differences in surface morphol-
ogy will be discussed below.
Figure 4 shows the variation in the temperature of the
sample when it reticulates 共TR兲 and when the scattered inten-
sity becomes maximum 共Tmax兲. Temperature is estimated
considering that the deposited power to the sample during
the time required for reticulation or maxima is utilized to
raise the temperature. There are small variations in the values
of these temperatures for different power densities to the
FIG. 5. 共a兲 Schematic diagram of the model used for three-layer simulation.
wafer, but the variations are not systematic. The average
共b兲 Schematic picture of the process of reticulation.
value of TR is found to be 141.82 ° C for 248 nm and it is
117.87 ° C for 193 nm PR. Glass transition temperature 共Tg兲
of 248 nm PR is ⬃140 ° C and that for 193 nm PR is tain time roughness suddenly decreases when the tempera-
⬃175 ° C. The value of TR for 248 nm PR is closely corre- ture reaches Tmax, which may be due to melting of the ma-
lated with its glass transition temperature; whereas it is much terial at this temperature.
lower than Tg for 193 nm PR. From ellipsometric ⌿-⌬ it is
noticed that there is a sharp increase in the value of ⌬ few 2. Simulation of ellipsometric ⌿-⌬ using three-layer
seconds prior to the reticulation, which implies a strong ex- model and effective medium approximation
pansion and it occurs at an average temperature of The real-time ellipsometric ⌿-⌬ values obtained with
102.01 ° C. This temperature is close to the Tg of polymeth- the PR materials during plasma processing show conven-
ylmethacrylate 共PMMA兲, which has the same polymer chain tional etching behavior before the point of reticulation. This
structure as 193 nm PR.6 This type of change in ⌬ before can be simulated easily using the known values of the optical
reticulation is not noticed in case of 248 nm PR. constants of the materials. After reticulation, a very different
The glass transition temperature of the untreated 193 nm characteristic behavior is seen, which is modeled in the fol-
PR is much higher 共175 ° C兲 than its base polymer PMMA lowing. To understand the mechanism of reticulation the el-
共100 ° C兲 since it contains adamantyl group in its structure. lipsometric ⌿-⌬ curves are simulated using a three-layer
When we expose the material to the plasma, photoacid gen- model.20,21 The ⌿-⌬ curves for the process for which the
erator 共PAG兲 generates acid due to plasma UV exposure. Due power density to the substrate is 0.435 W / cm2 are consid-
to reaction with the photogenerated acid, the adamantyl ered for simulation. Figure 5共a兲 shows the schematic diagram
group is removed resulting in deprotection and conversion of of the three-layer model that is used for simulation of the
ester into carboxylic acid.6 Due to removal of adamantyl ⌿-⌬ curves. The top layer is the carbon-rich modified layer
group the glass transition temperature of the material is again that forms during the first few seconds of plasma exposure
reduced and hence strong expansion and then reticulation due to ion bombardment and has optical index N M and ex-
occurs at a lower temperature 共close to the Tg of PMMA兲. tinction coefficient K M . The second layer from the top is the
The average value Tmax is found to be 292.5 ° C for 248 rough layer that forms after reticulation with optical con-
nm and 232.57 ° C for 193 nm PR, respectively. When the stants NR and KR. The index and extinction coefficient of the
material reticulates, roughness grows rapidly and after a cer- rough layer is estimated using Bruggeman’s effective me-
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 013311-5 Pal et al. J. Appl. Phys. 105, 013311 共2009兲

10
AB - fast etching, modified layer formation 248 nm

(A.U.)
F (a) F
330 BC - slower etching C
C - reticulation
CD - expansion, faster growth of roughness 8
E

1/2
325 DE - solvent loss

(Scattered Intensity)
EF - expansion, slower growth of roughness
6
320 D
E 4
∆

315
2
310 D B C
A B

0 450
305 (a) A
0

(b)
10 20 30 40

248 nm, Measurement

250
30 F 35 40AB - fast
45etching,
50modified
55 layer 60
formation
65 C 70 400
330 BC - slower etching

Roughness (nm)

Thickness (nm)
C - reticulation 200
CD - expansion, faster growth of roughness
325 DE - solvent loss
150 350
EF - expansion, slower growth of roughness

320 100
E
300
∆

315 50

0 250
310 D B 0
(c) 10 20 30 40

0.15
1.55
305 (b) Simulation A

30 35 40 45 50 55 60 65 70 1.50 0.10

Ψ
n

k
FIG. 6. Ellipsometric ⌿-⌬ curve for reticulated 248 nm PR: 共a兲 measure- 1.45 0.05
ment and 共b兲 simulation.

dium approximation where the effective medium is consid-
ered to be composed of 50% air and 50% bulk film
material.20,21 The third layer in the three-layer model is the
bulk film on the silicon substrate. The optical index and ex-
tinction coefficient for this layer is taken as NF and KF. A
schematic picture of the process of reticulation is presented
in Fig. 5共b兲, which shows how the changes in the films take
place when reticulation occurs.
When the material reticulates, too many unknown vari-
ables arise and hence it is difficult to simulate such situation.
So, to simulate the ⌿-⌬ curves for reticulated samples we
first considered that the maximum roughness that developed
after reticulation is known from AFM measurements and val-
ues of the roughness variation with time are estimated from
the scattered light measurement. While simulating the ⌿-⌬
curves, these values of roughness are inserted as known vari-
ables and hence other variables 共thickness, index, and extinc-
tion coefficient兲 are estimated.
The measured and simulated ⌿-⌬ curves for 248 nm PR
are presented in Figs. 6共a兲 and 6共b兲, respectively. At point A,
plasma is turned on and value of ⌬ increases very fast in the
region AB. This is followed by the region BC where there is
a slower increase in ⌬ but a faster increase in ⌿ as compared
to the region AB; however, the rate of increase in ⌬ is still
much higher than that of ⌿ in the region BC. At point C
reticulation occurs. After C, the ⌿-⌬ curve diverts from its
normal path and instead moves fast in the reverse direction.
For the region DE there is a sudden transition, which is fol-
lowed by the region EF where at point F the maximum
roughness has developed. We have simulated the ⌿-⌬ curve
up to the point F where the maximum roughness is seen. This
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1.40
AB C D E F 0.00
0 10 20 30 40
Plasma Exposure Time (s)
FIG. 7. 共a兲 Square root of the scattered intensity vs plasma exposure time
for reticulated 248 nm PR when treated in argon plasma at a current density
of 0.435 W / cm2. 共b兲 Simulated values of the variation in roughness and
thickness of the same sample and 共c兲 simulated values of the variation in
index and extinction coefficient of the same sample.
interval from the onset of reticulation to the maximum of
roughness is most important for an understanding of the re-
ticulation mechanism.
Variation in the measured scattered light intensity 共a兲 and
values of roughness, thickness 共b兲, and optical constants 共c兲
obtained from the simulation of the ellipsometry data versus
plasma exposure time are shown in Fig. 7. ⌻he changes that
occur in the different regions of the ⌿-⌬ curve are clear
from the simulated values of the thickness and roughness
关Fig. 7共b兲兴 and index and extinction coefficient 关Fig. 7共c兲兴. In
the region AB fast etching occurs and simultaneously a
modified layer forms. From the simulation of the ⌿-⌬ curve
the thickness of the modified layer is found to be 4.25 nm
with an index of 2.2 and extinction coefficient of 0.165. After
the modified layer has been formed, the etch rate becomes
smaller in the region BC since ions cannot penetrate beyond
the modified layer. At point C the temperature of the material
reaches the glass transition temperature and reticulation oc-
curs. In the region CD pronounced surface roughness devel-
ops. Roughness development is accompanied by a strong ex-
pansion of the material, which is seen as a thickness increase
after the onset of reticulation. The effect of film expansion
 013311-6 Pal et al. J. Appl. Phys. 105, 013311 共2009兲

Baked 100
(a) 193 nm, Measurement
Unbaked
345
G F
E
80
330 D
∆

C
B A
60

∆
315 AB - fast etching, modified layer formation
BC - etching
E CD - etching, expansion
D - reticulation
D
DE - fast growth of roughness
40 60 40 EF - growth of roughness, etching
FG - slower growth of roughness, etching
Ψ
FIG. 8. Effect of sample baking on the variation in ellipsometric ⌿-⌬ for 25
(b) 30 35 40 45 50 Simulation
55 60
248 nm PR.
G F
80 E
can also be noticed in the changes of the refractive index and D
the extinction coefficient. The index of the material is found
C A
to decrease while there is a small increase in the extinction 60 B

coefficient. In the region DE, a sudden decrease in the thick-
ness occurred. A possible reason of this decrease in thickness
may be evaporation of some material. To examine this point,
we have baked a sample for 2 h at a temperature of 75 ° C in
vacuum 共3 ⫻ 10−5 Torr兲 and studied its reticulation behavior.
Figure 8 shows the ⌿-⌬ curves for a baked and unbaked
sample of 248 nm PR treated in argon plasma. It has been
observed that the transition region DE that appears in the
⌿-⌬ curve of unbaked sample almost disappears when the
sample was baked. This supports the idea that the sudden
thickness decrease in the region DE is due to solvent loss.
Again, the boiling point of the solvent 共ethyl lactate兲 that is
mainly used in the 248 nm PR material is 154 ° C and we
have measured the temperature at the transition point D as
162 ° C, which is very close to the boiling point of the sol-
vent. This also confirms that solvent loss is the reason of
thickness loss at that point. In Ref. 22, M. J. May et al.
reported the results of TGA analysis for 248 nm PR, which
shows that there is a small decrease in weight at around
155 ° C, which should give another confirmation about sol-
vent loss.
In the region EF, expansion continues and roughness de-
velops at a slightly lower rate. Here the refractive index de-
creases due to expansion as the material becomes less dense
and also a significant increase in the extinction coefficient is
noticed, which may be due to changes in the light absorption
characteristics of the material introduced due to the effect of
high temperature.
We also simulated the ⌿-⌬ curve for the 193 nm PR.
The measured and simulated curves are presented in Figs.
9共a兲 and 9共b兲, respectively. To minimize the effect of sol-
vents the sample is initially baked at a temperature of 75 ° C
for 2 h and subsequently processed in the plasma. Similar to
the case of the 248 nm PR, there is a sharp change in the
region AB, followed by a region BC where slower changes
take place. Subsequently, region CD exhibits a sharp increase
in ⌬, with a slower change in ⌿. In the region DE, the ⌿-⌬
curve follows a reverse path where a strong decrease in the
⌿ value is noticed. This is followed by region EF, where ⌬
changes at a slower rate. At the point F the ⌿ value again
decreases fast with a very slow change in the ⌬. The varia-
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∆
AB - fast etching, modified layer formation
BC - etching
CD - etching, expansion
D - reticulation
40 DE - fast growth of roughness
EF - growth of roughness, etching
FG - slower growth of roughness, etching
25 30 35 40 45 50 55 60
Ψ
FIG. 9. Ellipsometric ⌿-⌬ curve for reticulated 193 nm PR: 共a兲 measure-
ment and 共b兲 simulation.
tion in the scattered intensity and the simulated thickness,
roughness, and optical constants with plasma exposure time
are compared and presented in Fig. 10. From Fig. 10共b兲 it is
clear that in the region AB very high rate etching occurs and
simultaneously a modified layer forms. The thickness of the
modified layer is found to be 4.9 nm with an index of 1.80
and extinction coefficient of 0.055. This region is followed
by region BC, where thickness decreases at a slower rate
with the modified layer established. In region CD, expansion
of the material occurs and the index decreases though at this
point reticulation does not occur 关Fig. 10共c兲兴. At point D, the
film reticulates and roughness develops very fast in region
DE, with the film thickness decreasing. So, in 193 nm PR
when the material reaches its Tg it at first expands and then
reticulates, but in 248 nm PR reticulation and expansion oc-
curs simultaneously. In the region EF roughness develops at
a slower rate. The slower rate of roughness development in
the region EF may be due to other simultaneous change in
the material, e.g., material may be lost using some of the
deposited energy for this process. In regions EF and FG, the
etch rate is found to be similar but the rate of increase in
roughness is slightly lower in FG. In this region, surface
roughness may develop further due to selective etching of
one material over another from the surface layer formed by
mixing of the modified and unmodified bulk material. A
small increase in extinction coefficient is seen for FG, which
may be due to some modification in the material that occurs
at high temperature, but it is much lower than seen for 248
nm PR.
The above observations suggest the following model of
reticulation: During first few seconds of plasma exposure a
 013311-7 Pal et al. J. Appl. Phys. 105, 013311 共2009兲

(A.U.)
193 nm of materials of the weak modified surface layer and the un-
(a) F
4 modified bulk material that penetrates the surface as a result
E
1/2
(Scattered Intensity) of strong chain motion when the temperature of the material
3 exceeds its glass transition temperature. The differences in
surface morphology seen in the AFM images of Fig. 3 are
2 consistent with these differences in reticulation behavior.
We generally observed that the roughness that develops
1 D for 248 nm PR is much lower than that seen for 193 nm PR
C
A B if during processing the materials are kept at a sample tem-
0 perature of 10 ° C. Conversely, when the temperature of the
0
(b) 5 10 15 20 25 30 400
samples was allowed to increase due to ion bombardment
80 during plasma exposure, the 248 nm PR showed much
Roughness (nm)

greater roughness than the 193 nm PR. The roughness for-

Thickness (nm)
60 360 mation processes are completely different at the two tem-
peratures, and due to selective etching of material for the 193
40
nm PR when kept at 10 ° C.6
320
20
B. Ex situ study of the light scattering

0 280 Figure 11共a兲 shows the dependence of 冑I on z for

0 (c) 5 10 15 20 25 30 samples with very large ranges of roughness starting from
1.50 0.015 few nanometers to few hundred nanometers. The relationship
冑I versus z still holds for these samples with a very small-
scale roughness to a very large roughness of up to 200 nm.
0.010
1.45 The scattering of laser light by these samples is studied with
k
n

an angle of incidence of 72° and the scattered light is re-

1.40
A B C D
0 5 10 15
Plasma Exposure Time (s)
FIG. 10. Square root of the scattered intensity vs plasma exposure time for
reticulated 193 nm photoresist when treated in argon plasma at a current
density of 0.435 W / cm2. 共b兲 Simulated values of the variation in roughness
and thickness of the same sample and 共c兲 simulated values of the variation in
index and extinction coefficient of the same sample.
carbon rich modified layer forms on the surface of the film
due to ion bombardment. This layer has a very high com-
pressive stress, which develops during its formation. When
the material attains its glass transition temperature and poly-
mer chain motion begins, the modified layer looses its sup-
port from the bulk material. Due to the compressive stress,
the surface layer becomes deformed and surface roughness
starts to develop. Growth of roughness is enhanced by the
strong expansion of the material and pressure induced by
polymer chain motion.
The basic mechanism of reticulation of 193 nm and 248
nm PR are similar, but there are some differences. It is clear
from the simulation of ellipsometric ⌿-⌬ that the modified
layer that forms in case of 248 nm PR is stronger than for the
193 nm PR. This suggests that the compressive stress that
develops for 248 nm PR will be greater and can be explained
by formation of a tough cross linked layer, whereas for 193
nm material chain scissioning is important and a weakly con-
nected modified surface layer forms. For 248 nm PR, the
surface layer becomes deformed when the material reticu-
lates but still remains intact, whereas for the 193 nm PR a
highly fragmented surface forms that may be due to mixing
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0.005
corded at an angle of 90° with the plane of incidence and 45°
with the surface normal. The samples with very high rough-
0.000 ness are reticulated 193 and 248 nm PRs treated in argon
E F G
20 25 30
plasma. For ex situ time resolved studies, we used a shutter
approach18,19 to treat the films in a gradient exposure mode
for time durations of 0–60 s. Using this approach, it is pos-
sible to expose different parts of the same sample for differ-
ent amounts of times. The materials are exposed to
Argon/C4F8 共90%/10%兲 discharges produced with a source
power of 1000 W and a substrate bias of ⫺100 V at a gas
pressure of 10 mTorr. The growth of roughness with plasma
exposure time for these materials was studied in detail in an
earlier work from this group.6 For 193 nm PR, the roughness
grows initially at a faster rate and after 40 s of exposure time
the rate of roughening slows down almost saturating after
around 55 s. The model polymer RADA also shows similar
behavior but the rate of growth of roughness and the maxi-
mum value of roughness is much lower in case of RADA.
Figure 11共b兲 shows the dependence of the scattered intensity
on plasma exposure time for 193 nm PR and RADA for the
above conditions. The scattered light intensity shows signifi-
cant change with the plasma exposure time. RADA shows
gradual increase in scattering intensity with an increase in
the plasma exposure time and at higher exposure times the
scattered intensity tends to saturate. The rates of change in
scattered light intensity and the highest level of the intensity
are lower for RADA. The 193 nm PR shows some different
behaviors in the initial few seconds of exposure. The scat-
tered light intensity initially decreases up to 10 s and after
that it starts increasing and ultimately tends to saturate as
expected. It is clear from the AFM results6 that the roughness
starts to develop from the very beginning of the plasma ex-
posure. We can explain the initial decrease in the scattered
 013311-8 Pal et al. J. Appl. Phys. 105, 013311 共2009兲

(a) 248 nm (c)

(A.U.)

(A.U.)
40 Ar 2.0

1/2

1/2
(Scattered Intensity)

(Scattered Intensity)
1.5 Ar/C4F8
193 nm Ar
20 Ar 1.0

0.5 RADA
193 nm
Ar/C4F8 Polystyrene
0 0.0
0 50 100 150 200 0 2 4 6 8 10
Roughness (nm) Roughness (nm)
2.5 1.0
Ar/C4F8 193 nm, Real time, Ar
(b) (d)
(A.U.)

(A.U.)
2.0
1/2

1/2
(Scattered Intensity)

(Scattered Intensity)
1.5
0.5

1.0

RADA
0.5 193 nm
0.0
0 10 20 30 40 50 60 0 20 40 60 80 100 120
Plasma Exposure Time (s) Plasma Exposure Time (s)

(e)

FIG. 11. 共Color online兲 共a兲 Square root of the scattered intensity vs rms roughness for the samples with wide range of roughness, 共b兲 Variation in the square
root of the scattered intensity with plasma exposure time for gradient exposed samples. 共c兲 Square root of the scattered intensity vs rms roughness for gradient
exposed samples. 共d兲 Real-time measurement of the laser light scattering from 193 nm PR treated in argon plasma with sample cooling and 共e兲 AFM image
of the 193 nm PR treated in argon plasma for 120 s with sample cooling.

light intensity by the significant change in the light absorp- We have used an angle of incidence of 30° for these samples
tion characteristics of the material. Since 193 nm PR con- and for better resolution a smaller laser spot size is more
tains a PAG, during the initial plasma exposure the PAG effective. It has been found that the intensity and roughness
generates acid due to plasma UV radiation. The PR material follows the 冑I ⬀ z relationship with some discrepancy in case
absorbs more light and hence the scattered light intensity of 193 nm PR that may be due the effect described earlier.
decreases. Since the other material, RADA does not contain Though the relationship is linear, for different materials there
are differences in the gradient of 冑I versus z.
any PAG, it does not show this drop in scattered light inten-
sity at the beginning of plasma exposure. Figure 11共c兲 com-
From this observation, it may be inferred that laser light
pares the variation in the square root of the scattered inten-
sity with rms roughness of the films. Solid circles in this scattering can be used as a diagnostic to study small-scale
figure represent the scattered light intensity variation with surface roughness development in polymer films during pro-
roughness for polystyrene films treated in argon plasma at cessing. Since the modified layer that forms on top of the PR
different self-biases. Roughness of these samples is around 1 film depends on the plasma chemistry and other processing
nm and lower. For recording the scattered light for such a conditions, we expect that the scattered intensity will vary
low roughness the angle of incidence needs to be very low. for PR films treated using different plasma conditions. Also,
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 013311-9 Pal et al.
the scattered intensity will be different for different materials
depending upon the optical properties of the materials. For
quantitative measurement it may be possible to estimate the
roughness by comparing the light scattered from a sample
with the scattering with a similar sample of known rough-
ness, but the material dependence and plasma chemistry and
processing condition dependence will need to be considered.
The scattering intensity also depends on the correlation
length, which may become a factor if correlation length
changes significantly due to plasma treatment.12 Interference
between the light scattered from the film surface and that
scattered from the substrate surface is another factor that
may become significant when the roughness level is very low
or comparable to the substrate roughness.
C. Real-time study of the light scattering with sample
cooling to observe growth of very small scale
roughness
We have studied surface roughness development in real-
time for 193 nm PR film treated in argon plasma for 120 s
for a source power of 400 W, substrate bias of ⫺100 V at a
pressure of 12 mTorr with a flow rate of 40 SCCM. Figure
11共d兲 represents the variation in the square root of the scat-
tered light intensity recorded in real-time with plasma expo-
sure time during the process. AFM image of the same sample
after 120 s of exposure is presented in Fig. 11共e兲, which
shows rms roughness of 10.32 nm. It is found that at the time
when plasma turns on the scattered light intensity slightly
increases, which may be due to broadening of the spectral
line when the plasma turns on. After this initial increase the
scattered light intensity drops during the next few seconds as
observed in case of gradient exposed samples and described
in Sec. III B. The initial drop in intensity that is observed is
due to increase in the light absorption as a result of the gen-
eration of acid as plasma UV radiation interacts with the
PAG that is present in this material. However, after this drop,
intensity starts increasing as roughness develops and at
around 90 s of exposure time the intensity tends to saturate.
The behavior of growth and saturation of the scattered light
is similar to that observed in case of the AFM measurements
of rms roughness as described earlier. From this observation
it may be inferred that for qualitative understanding of the
growth of roughness in real-time this technique may be use-
ful if by some arrangement the signal to noise ratio can be
improved, but for quantitative estimation of very low rough-
ness there are some limitations as discussed in this and in the
earlier sections.
IV. CONCLUSIONS
The present work demonstrates that by measuring the
scattered He–Ne laser light intensity it is possible to study
the growth of surface roughness on photoresists starting from
the very beginning of the plasma process when the roughness
is in the subnanometer range. We also show that the mea-
surement of light intensity scattered from a PR surface dur-
ing reticulation, in combination with real-time ellipsometry
and AFM provides significant insight into the mechanism of
PR reticulation. The reticulation process is found to be ac-
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J. Appl. Phys. 105, 013311 共2009兲
companied by strong material expansion. The roughness that
develops due to reticulation depends on the properties of the
materials and the plasma-altered surface region. For 248 nm
PR the modified layer is retained even after reticulation and
the roughness that develops is higher than for 193 nm PR. In
193 nm PR, a mixed layer consisting of the modified layer
and the unmodified bulk material, forms on the top surface
after reticulation. From this observation, it may be inferred
that the material that contains aromatic rings in its backbone
and cross links as a result of plasma exposure develops more
roughness when it reticulates and forms a surface morphol-
ogy that is very distinct from that formed for a material for
which chain scissioning is an important radiation response.
ACKNOWLEDGMENTS
One of the authors 共A.R.P.兲 acknowledges the support
provided by the Department of Science and Technology,
Government of India and the Institute of Advanced Study in
Science and Technology, Guwahati-781035, India for award-
ing him the BOYSCAST fellowship and gratefully acknowl-
edges University of Maryland for hosting him. R.L.B., F.W.,
S.E., T.L., R.P., and G.S.O. gratefully acknowledge support
by the National Science Foundation under Award Nos. CTS-
0506988, DMR-0406120, and DMR 0705953.
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