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Mo Si Multilayers For EUV Lithography by Ion Beam
Mo Si Multilayers For EUV Lithography by Ion Beam
Abstract
Mo/Si multilayers for applications in extreme ultraviolet (EUV) lithography have been prepared on Si wafer
substrates using ion beam deposition. The multilayers were characterised by transmission electron microscopy,
secondary ion mass spectroscopy, atomic force microscopy, photoelectron spectroscopy, X-ray reflectometry at grazing
incidence, and EUV-reflectivity measurements at nearly normal incidence. The surface and the interfaces of the
multilayers are rather smooth with only small roughness. The material properties of the layers are characterised by
some intermixing and silicide formation at the Mo–Si interfaces and a polycrystalline grain structure of the Mo layers,
which is in agreement with prior studies. Appearance of multilayer diffraction spots, well-resolved Kiessig fringes and
other diffraction evidence indicate very good coherence of the wave fields and in this manner a good reproducibility of
the multilayer period of 6.7 nm. Normal incidence peak reflectivities of 64–65% in the EUV spectral range were
routinely obtained at 13.4 nm wavelength. This reflectivity value and the formation of an EUV standing wave field are
confirmed using photoelectron spectroscopy, and an application for defect particle analysis is proposed. The obtained
results are discussed in comparison to literature data of multilayers prepared by other deposition techniques and
considering new attempts of interface engineering.
r 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Multilayers; Mo; Si; EUV reflectivity; X-ray reflectivity; Ion beam sputter deposition; SIMS; TEM; Photoemission; Soft
X-ray standing waves
1. Introduction
0042-207X/03/$ - see front matter r 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0042-207X(02)00768-6
408 T. Chass!e et al. / Vacuum 71 (2003) 407–415
Base Flange
Auxiliary Anode
Iron Yoke with Gas Supply
Quartz Cup
Screen Grid
Accelerator Grid
Resonance Region
λ/4 Antenna
Electric Field
Magnetic Field
Aluminium Gasket
Grid Insulation
Breakthrough Protection
Permanent Magnets
Ceramics Lining
Fig. 2. ECR source as developed for ion beam assisted deposition and ion beam figuring.
002
-
111 Mo
α-Si
000 - Si
220
(a)
5 nm
S
(a)
0.22
(b)
Fig. 5. (a) High-resolution TEM picture (200 kV) of an Mo/Si
multiayer on a Si wafer, showing the Mo and Si layers near the
c-Si substrate. Arrows indicate regions of Mo–Si intermixing,
which results in an interface transition zone. (b) HR-TEM
picture showing the crystalline grain substructure of Mo layers
within a Mo/Si multilayer. The layers and the layer spacing in
crystalline Mo grains are indicated.
(b)
Fig. 4. (a) Diffraction pattern from a Mo/Si multilayer on due to the deposited multilayer structure. Please,
Si(0 0 1) obtained by TEM. (b) Zoom of the pattern from (a) note that such a sequence of spots can only be
near the (0 0 0) reflex of the c-Si substrate showing the resolved in case of a highly reproducible film
diffraction spots from the multilayer.
thickness and thus a good periodicity of the
diffracting system. The spot distance in reciprocal
excellent control of the individual layers and the space allows to trace back to the multilayer period
smooth interfaces. Fig. 4 displays related diffrac- in real space, which gives us about 6.7 nm, in good
tion patterns of the transmitted high-energy accordance to the complementary data as revealed
electrons. The crystalline structure of the Si from the layer spacings in high-resolution TEM
substrate is easily recognised. However, near the pictures like in Fig. 5. The first picture in Fig. 5a
(0 0 0) reflex of the Si wafer in Fig. 4a, a series of shows part of the substrate together with the
smaller spots extend towards the (0 0 2) reflex. nearest Si and Mo layers. The crystalline structure
These smaller spots occur much more clearly in of the Si wafer provides the appropriate length
Fig. 4b, which displays a zoom to the former one scale to estimate the layer thicknesses. The dark
(Fig. 4a). This sequence of spots near (0 0 0) of Si is Mo layers appear broader than expected from the
T. Chass!e et al. / Vacuum 71 (2003) 407–415 411
preadjusted thickness values. While the Mo/Si interface compared to the other one. Traces of B
interfaces within the field of view appear rather and Cr contaminants were also observed, but due
smooth, nevertheless transition regions (dark grey) to the oxygen probing ions no reliable information
occur between the centre of the Mo layers (dark) could be obtained regarding oxygen content within
and the Si layers (bright), which indicate an the multilayer.
intermixing of Mo and Si, most probably due to
silicide formation. The width of this intermixing 3.3. XRR
region seems to be larger at the Mo on Si interface
than at the Si on Mo interface, as may be revealed, X-ray reflectivity (XRR) measurements at graz-
e.g. by looking at the first Mo layer from substrate. ing incidence were performed using Cu Ka
The Si layers clearly lack any features of crystalline radiation. Fig. 7 shows the experimental low-angle
structure and are therefore amorphous. However, XRR curve of a Mo/Si multilayer in comparison
detailed look at the Mo layers in the Fig. 5b to a simulation. The relative intensity of the first
demonstrates presence of crystalline grain struc- Bragg peak corresponds to a high reflectivity of
ture, and thus the Mo layers may be regarded to be 96.2% at this wavelength of 0.154 nm, again
essentially polycrystalline. indicating a low interface roughness of the layers.
The appearance of the fine structure between the
3.2. SIMS Bragg peaks due to the Kiessig fringes further
demonstrates the excellent periodicity within the
Secondary ion mass spectroscopy (SIMS) has layer stack [18]. The Darwin-type shape of the first
been used for elemental depth profiling. A SIMS Bragg peak is another direct hint for the high
depth profile performed with 1 keV O2 ions using coherence of the wave field within the layer stack.
an ATOMIKA SYS 4500 instrument is shown in The simulation result correlates very well with the
Fig. 6. The complete multilayer of about 340 nm measured data. However, certain important con-
thickness may be investigated with comparable clusions may be drawn from the fits. First, a four-
maximum to minimum intensity contrast ratio, layer structure consisting of Mo, Si, and two Mo–
demonstrating the excellent resolving power. The Si intermixing layers at the interfaces rather than a
relative thicknesses of Mo and Si layers also seem simple two-layer structure (Mo–Si) had to be
to be inverted but note that corrections for included in the fits [19]. Typical thickness data
material-dependent sputter rates were omitted from the fits are 2.9 nm Mo, 3.3 nm Si, and a total
here. An evident shoulder in the individual Mo of 0.5 nm Mo–Si, while interface roughness values
layer profiles at the Mo on Si interface indicates of less than 1.2 nm were determined. This results in
(a) an intermixing of both elements and (b) a multilayer period of 6.7 nm, again in good
also a broader intermixing zone at this particular agreement to the above mentioned HR-TEM and
TED data.
92
100 Mo
3.4. AFM
Cu Kα radiation
5 multilayer 1286 (50 Mo/Si layers)
10
4
10
Intensity [cps]
3
10
2
10
Fit
1
10
250 nm 3 nm 250 nm 3 nm
0 nm 0 nm
(a) (b)
Fig. 8. AFM pictures taken from different Mo/Si multilayers. The height scale and characteristic roughness parameters are also
provided.
number of white hillocks indicates only local pro- 12.5–14 nm are shown in Fig. 9. Data were
trusions as expressed by typical peak-valley rough- recorded at an incidence angle of 1.51. The
ness values of only 2–3 nm. There is no evidence for maximum reflectivity of 64.8% is achieved at
larger protrusions in these small-area pictures. 13.4 nm, and the half width of the reflectivity curve
is about 0.52 nm in this case. We have routinely
3.5. EUV reflectivity obtained peak reflectivities between 64% and 65%
for different investigated Mo/Si multilayer sam-
One of the most important multilayer properties ples. The two reflectivity curves shown in Fig. 9
is the near-normal incidence reflectivity. This has represent different analysis spots on the same
been measured at the PTB beamline at BESSY II multilayer. The observed slight shift of the
in Berlin using an EUV reflectometer [20]. reflectivity peaks indicates that the lateral homo-
Representative reflectivity curves for the range geneity still needs some further optimisation.
T. Chass!e et al. / Vacuum 71 (2003) 407–415 413
0.7
0.6
0.5
0.4
R
0.3
0.2
0.1
0.0
12.50 12.75 13.00 13.25 13.50 13.75 14.00 14.25
λ [nm]
Fig. 9. EUV-reflectivity curves measured from a Mo/Si multilayer using the PTB equipment at BESSY II. The incidence angle is 1.51.
mainly because of the unavailability of adequate induced smoothing [23]. Nevertheless, the peak
equipment for particle identification and analysis reflectivities R reported above for IBD in fact
significantly below 100 nm particle size. However, belong to the highest values reported so far and, in
we suggest, that the concept of using a secondary particular, for IBD. They nearly meet the current
signal like photoemission intensity excited by requirements of EUV lithography, which have
the standing wave field as described above in been announced by ITRS [8,15] for 2001 with
combination with an imaging technique like, RB65% but need to be improved to B70% soon.
e.g. PEEM may be extremely useful for locat- Slightly superior peak reflectivities of up to 68–
ing and identifying defects or particle contamina- 69% have already been achieved using PLD,
tions of the multilayers just in the interesting magnetron sputtering, and electron beam deposi-
length scale down to 30 nm. This could become a tion [9–13].
benefit for contamination inspection of mask The recent results with up to 70% peak
blanks. reflectivity in the EUV range have taken advantage
of interface engineering. In particular, ultrathin
interface layers of, e.g. B4C [15] or Mo2C [24] or
4. Discussion substructuring of the Mo layer [14] have been used
to improve interface roughness, suppress intermix-
Finally, our results will be compared to the data ing at the interface, reduce stress within the
from literature, which mostly relate to multilayers multilayer structures, and improve the tempera-
deposited using electron beam evaporation or ture (or life time) stability of the multilayers.
magnetron sputtering. Regarding material proper- Insertion of ultrathin EUV-transparent interface
ties, our results fit quite well into these data. The layers in order to prevent silicide formation
formation of Mo–Si intermixing layers at the resulted in significant improvements of thermal
interfaces with an asymmetric thickness as de- stability of the multilayers but at the expense of
scribed above is observed quite generally and slightly lower reflectivities in most cases. For
evidently occurs independent of the deposition instance, Mo2C interface layers and a complete
technique. Recently, a transition from amorphous substitution of the Mo layer have been used in
to polycrystalline Mo layers has been detected, order to accomplish this purpose [24]. However,
which takes place at a Mo thickness of about 2 nm application of boron carbide (B4C) interface layers
[21]. This also fits well to the polycrystalline grain resulted in an improvement of the peak reflectivity
structure observed in our and also other TEM to 70% at 13.5 nm [15]. Boron carbide is a low Z
data from Mo/Si multilayers designed for peak material that reduces the silicide formation and
reflectivity at 13.4 nm, which have Mo thicknesses increases the reflectivity but also reduces the heat
above this limit, typically. While this general resistance of the multilayers.
picture of the material properties of the layers Such interface engineering attempts have not
and their interfaces is quite consistent, some been included in our IBD technology yet. There
difference in the reported intermixing and interface are still plenty of opportunities to optimise the
roughness remain, which may be due to the IBD process for the Mo and Si depositions, e.g. by
different deposition techniques and the reached application of the assist source for ion beam
state of the related deposition technologies [9–15]. polishing or a special temperature regime, which
For instance, in situ control of the deposition may permit further improvement of the Mo/Si
process by Cu–K reflectivities and ion beam multilayer properties obtained by IBD. In sum-
polishing steps following the deposition of indivi- mary, our results clearly demonstrate that high-
dual layers permit efficient growth control result- quality Mo/Si multilayers can be prepared by IBD.
ing in improved reflectivities [19,22]. Further The technology for the IBD process is going to
improvements regarding layer smoothness may close up remaining gaps to other multilayer
be expected from a temperature control during deposition techniques and will surely be able to
deposition in order to benefit from diffusion- compete successfully.
T. Chass!e et al. / Vacuum 71 (2003) 407–415 415