Structure and composition of zirconium carbide thin-film grown by ion beam sputtering

for optical applications

Amol Singh, Mohammed H. Modi, Rajnish Dhawan, and G. S. Lodha

Citation: AIP Conference Proceedings 1591, 869 (2014); doi: 10.1063/1.4872785

View online: http://dx.doi.org/10.1063/1.4872785
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 Corrigendum: Structure and Composition of Zirconium Carbide Thin-Film Grown by Ion Beam
Sputtering for Optical Applications, Amol Singh, Mohammed H. Modi, Rajnish Dhawan and
G. S. Lodha, AIP Conf. Proc. 1591, 869 (2014)

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 Structure and Composition of Zirconium Carbide Thin-Film
Grown by Ion Beam Sputtering for Optical Applications
Amol Singh1, Mohammed.H.Modi1,*, Rajnish Dhawan1, G.S.Lodha1
1
X-ray Optics Section, ISU Division, Raja Ramanna Centre for Advanced Technology, Indore 452 013, India
*
Email Corresponding Author: modimh@rrcat.gov.in

Abstract. Thin film of compound material ZrC was deposited on Si (100) wafer using ion beam sputtering method. The
deposition was carried out at room temperature and at base pressure of 3×10−5 Pa. X-ray photoelectron spectroscopy (XPS)
measurements were performed for determining the surface chemical compositions. Grazing incidence x-ray reflectivity
(GIXRR) measurements were performed to study the film thickness, roughness and density. From GIXRR curve roughness
value of the film was found less than 1 nm indicating smooth surface morphology. Films density was found 6.51 g/cm3,
which is close to bulk density. Atomic force microscopy (AFM) measurements were performed to check the surface
morphology. AFM investigation showed that the film surface is smooth, which corroborate the GIXRR data.
Keywords: Thin films, Ion beam evaporation, X-ray reflectivity, Multilayers, X-ray optics.
PACS: 68.60.Bs, 81.15.Jj, 61.05.cm, 78.67.Pt, 41.50.+h

INTRODUCTION
Multilayers comprised of low Z/ high Z elements are
widely used in variety of applications in soft x-ray region.
Such multilayer poses a severe drawback of high
reactivity among the constituent elements. Formation of
silicide in Si based multilayers (Mo/Si, W/Si, Nb/Si etc)
is a common problem. These multilayers have very poor
thermal stability because of intermixing of layers in high
heat load environment. To overcome the inter-diffusion a
barrier layer (of carbon) is deposited in between Mo and
Si, which reduces reflectivity in significant amount. Apart
from a barrier layer many authors have used compound
materials to prevent interfacial reaction. Recently NbC/Si
multilayer was proposed as a replacement of Mo/Si
multilayer. This new combination shows high thermal
stability and equivalent reflectivity performance as one
obtained with Mo/Si structure1. The NbC/Si multilayer
structure was reported to be stable upto 700°C annealing
temperature. A. F. Jankowski et al. have reported W/B4C
a better combination over W/C multilayers in terms of
thermal stability2. Qi Zhong et al. have reported Zr/Al
multilayer a good combination for the use of EUV
applications, but Zr/Al has very poor thermal stability
after 200°C3. Intermixing and Al-Zr alloy formation are
reported after 200°C in Zr/Al multilayers. ZrC can be a
good substitute for Zr. In optical applications composition
and microstructure of the deposited films are critical and
must be investigated to improve the quality of thin films.
ZrC have some excellent properties which makes it very
attractive in variety of demanding applications, such as
very high melting point (Tm=3445°C), very high
hardness (30-35 GPa), high thermo chemical stability,
high wear resistance, high optical emissivity, etc.4.
Solid State Physics
AIP Conf. Proc. 1591, 869-871 (2014); doi: 10.1063/1.4872785
© 2014 AIP Publishing LLC 978-0-7354-1225-5/$30.00
Deposition of high quality ZrC thin films are difficult due
to its high melting point, low evaporation and sputtering
rate, high reactivity of Zr with oxygen and water vapours.
Earlier several techniques are used for the deposition of
ZrC thin films such as physical vapor deposition,
chemical vapor deposition, dc magnetron sputtering, e-
beam evaporation, pulsed laser deposition (PLD) etc. In
PLD technique deposition of such material is quite
challenging because of very demanding deposition
condition such as excess substarte temperature and very
high laser fluence. A laser fluence around 10J/cm2 is
required which is quite challenging to be implemented.
ZrC thin film of thickness 300Ǻ was grown on Si
(100) substrate using ion beam sputtering method. Film
thickness, roughness and film density was measured
using Grazing incidence x-ray reflectivity (GIXRR)
technique. X-ray photoelectron spectroscopy (XPS)
technique was used for the surface elemental
composition; AFM measurements were performed to
investigate surface morphology.
EXPERIMENTAL
Thin film of ZrC of 300Ǻ was deposited on Si (100)
wafer using ion beam sputtering setup. Commercially
available sputtering target of ZrC having 99.99% purity
was used for the deposition. Prior to deposition the
system was evacuated to the base pressure of 3×10−5 Pa
and deposition was carried out at constant pressure of
6×10−2 Pa using Ar ions. The process parameters for
obtaining smooth and uniform ZrC film were optimized
by depositing various thin film samples where it was
found that the films deposited at 1000 V beam voltage
and a gas flow rate of 3 standard cubic centimeters gives
low roughness and uniform thickness film.

869

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 X-ray photoelectron spectroscopy (XPS) This decrement in film density can be explained by
measurements were carried using an Omicron EA-125 smaller crystalline grains compared with epitaxial films
photo electron spectrometer working at a base pressure of and increased grain boundary volume fraction and voids
~6.66×10-8 Pa. Al Kα radiation was used for the analysis, for the films. V. Cracium et al. have deposited ZrC thin
with the source operated at 10 kV anode voltage and 10 films for application in hard coating8. They achieved
mA emission current. density of 5.80 gm/cm3 at 30°C substrate temperature,
100 which is very low compared to bulk value. They have
ZrC 300 Angstrom
Measured
achieved highest density of 6.60 gm/cm3 at substrate
10-1
Fitted temperature 500°C. Near bulk desnty in ZrC film was
obtained in thick samples of 1650Å by PLD technique9 .
10-2 In the present case near bulk density was obtained in ZrC
film for very low thickness value of 300Ǻ. This shows
Reflectivity

10-3 that the ion beam sputtering technique can be used to

achieve near bulk density in the ZrC thin film after
10-4 systematic process optimization. RMS surface roughness
of ZrC film from the fitting of GIXRR data was found
less than 1nm.
10-5 1000
Measured
10-6 Fitted
0.0 0.5 1.0 1.5 2.0 2.5 900
Incidence angle (deg)
Figure 1 Measured and fitted GIXRR data of ZrC thin Intensity (arb units)
800
film. Vertical line shows the critical angle for ZrC.
700
GIXRR measurements in hard x-ray region were
performed using a BRUKER D-8 system consisting of θ - ZrC 3p3/2 ZrC 3p1/2
600
θ goniometer and x-ray source of Cu target at λ =1.54 Ǻ
Cu-Kα. Parratt formalism5 was used to analyse the Zr 3p1/2
reflectivity data. Effect of surface roughness was taken in 500
Zr 3p3/2
account using Novet-Croce model6. A nonlinear least- Zr Core ZrC 300 Angstom
square refinement routine based on the Genetic algorithm 400
315 320 325 330 335 340 345 350 355
was used to refine fitting parameters7.
AFM measurements were performed with a B.E.(eV)
Nanoscope III from Digital Instrument with super sharp
silicon nitride cantilever to probe different portion of the Figure 2 Measured and fitted XPS spectrum for Zr 3p
film surface. Measurements were carried out over 1 μm, 2 region acquired from as deposited ZrC thin film of
μm and 5 μm scale in close contact mode over 256×256 thickness 300 Å.
500
pixel area. The probe fixed on a small spring is scanned Measured
over the surface of the sample. The force between tip and Fitted
the surface was ~10-8 N. The relative position of tip and 450
the surface was adjusted by a feedback system in such a
Intensity (arb units)

way that the force remains constant.

400
RESULTS AND DISCUSSION
Figure 1 shows the measured and simulated GIXRR 350
curves of ZrC thin film. The well resolved Kiessig fringes C-C
(shown in Figure 1) suggest that the interfaces in the film
have a sharp density gradient and low roughness. GIXRR 300
data were fitted with assuming three layer model in
ZrC
Motofit software. The three layer model comprised of a Carbon Core ZrC 300A
250
~30-40 Ǻ native oxide SiO2 layer on the substarte, a ion 278 280 282 284 286 288 290 292
beam deposited ZrC layer and a third surface layer B.E.(eV)
formed due to contamination/oxidation in the ambient Figure 3 Measured and fitted XPS spectrum for C 1s
environment. After rigorous fitting the thickness of the region acquired from as deposited ZrC thin film of
ZrC film (including surface layer) was found to be 343Ǻ
The density of the film evaluated from the critical angle thickness 300 Å.
position as marked by vertical dashed line in the Figure 1
was found to be ~6.51 gm/cm3 which is slightly lower Chemical composition of the film was analysed using
than the bulk value (6.73 gm/cm3) of epitaxial ZrC films. XPS measurement. Figure 2 shows the high resolution

870

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 XPS spectra corresponding to Zr 3p region acquired from
the sample. XPS spectrum is fitted with four components.
A small peak at binding energy 343.4eV corresponds to
Zr 3p1/2. Peak position is taken from the elemental
library supplied with the XPS instrument. The second
peak with binding energy 346.96eV corresponds to ZrC
3p1/2. Another small peak with binding energy 329.7eV
(from elemental library) corresponds to Zr 3p3/2.
Similarly fourth peak with binding energy 333.23eV
corresponds to ZrC 3p3/2. No other peaks were observed
in the XPS spectrum indicating very less contamination
on the surface. Carbon 1s core spectrum of the same
sample is shown in Figure 3. The spectrum was fitted
with two components. One with binding energy 285.19eV
corresponding to C-C sp2 hybridization and other with
binding energy 282.10eV which corresponds to carbon
bonded to Zr. XPS investigation clearly indicates very
less amount of contamination in the films.
For analysing surface morphology, AFM
measurements were performed and are shown in Figure 4.
AFM images were taken at 1μ, 2μ and 5μ scales
respectively. AFM data clearly shows smooth surface
morphology. RMS roughness value was calculated from
all the images using WSXM software10. Roughness value
for 1μ×1μ image was 6.5Ǻ, for 2μ×2μ image roughness
was 7.1Ǻ and for 5μ×5μ roughness was found 8.1Ǻ.
Roughness calculated from GIXRR data and AFM
images are in close agreement. AFM data confirms that Figure 4 AFM 2D topography (left panel) and
film surface is smooth which is required for optical corresponding 3D reconstructed (right panel) images of
elements. ZrC thin film. Scan is performed in three ranges 1μ, 2μ
Our detailed study of GIXRR, XPS and AFM data and 5μ.
clearly indicates that ZrC thin film is grown with smooth
suface morphology with density very close to bulk value. REFERENCES
Further ZrC thin films of different thickness are grown to
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(2012).
2
A. F. Jankowski et al. J. Appl. Phys. 68, 5162-5168
CONCLUSIONS 3
(1990).
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ZrC thin film was deposited on Si substrate in high (2013).
vacuum conditions by ion beam sputtering technique. 4
V.Cracuin et al. J Eur. Cer. Soc. 33, 2223-2226 (2013).
GIXRR spectra indicated that the film density was around 5
L.G. Parratt, Phys. Rev. 95, 359-369 (1954).
6.51 gm/cm3, which is 95-97% of the tabulated bulk 6
L.Novet and P.Croce, Rev. Phys. Appl. 15, 761-779
value. AFM data suggest that the film has smooth surface (1980).
morphology. The study suggest that the ion beam 7
Nelson A, J. App. Cryst. 39, 273-276 (2006).
sputtering technique can be used to grow compound film 8
V. Cracium et al. J. Eur. Cer. Soci. 133, 2223-2226
of ZrC material having near bulk density and smooth (2013).
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10
ACKNOWLEDGEMENTS I. Horcas et al. Rev. Sci. Instr. 78, 013705 (1-8) (2007).

Authors are thankful to Dr. D. M. Phase Mr. A. D.

Wadikar for XPS measurements. Authors are thankful to
Dr. V. Ganesan and Mr Mohan Gangrade for AFM
measurements.

871

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