Magnetron sputtered epitaxial single-phase Ti 3 SiC 2 thin films

J.-P. Palmquist, U. Jansson, T. Seppänen, P. O. Å. Persson, J. Birch, L. Hultman, and P. Isberg

Citation: Applied Physics Letters 81, 835 (2002); doi: 10.1063/1.1494865

View online: http://dx.doi.org/10.1063/1.1494865
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/81/5?ver=pdfcov
Published by the AIP Publishing

Articles you may be interested in

Epitaxial growth of Ti3SiC2 thin films with basal planes parallel or orthogonal to the surface on α-SiC
Appl. Phys. Lett. 101, 021606 (2012); 10.1063/1.4737018

Epitaxial growth of lead zirconium titanate thin films on Ag buffered Si substrates using rf sputtering
Appl. Phys. Lett. 90, 172903 (2007); 10.1063/1.2731515

Phase stability of epitaxially grown Ti 2 Al N thin films

Appl. Phys. Lett. 89, 074101 (2006); 10.1063/1.2335681

Growth of Ti 3 SiC 2 thin films by elemental target magnetron sputtering

J. Appl. Phys. 96, 4817 (2004); 10.1063/1.1790571

Deposition of Ti 2 Al C and Ti 3 Al C 2 epitaxial films by magnetron sputtering

Appl. Phys. Lett. 85, 1066 (2004); 10.1063/1.1780597

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
152.2.176.242 On: Mon, 01 Dec 2014 02:12:49
 APPLIED PHYSICS LETTERS VOLUME 81, NUMBER 5 29 JULY 2002

Magnetron sputtered epitaxial single-phase Ti3 SiC2 thin films

J.-P. Palmquista) and U. Jansson
Uppsala University, Department of Materials Chemistry, The Ångström Laboratory,
P.O. Box 538 SE-751 21 Uppsala, Sweden
T. Seppänen, P. O. Å. Persson, J. Birch, and L. Hultman
Linköping University, Department of Physics, Thin Film Physics Division, SE-58183 Linköping, Sweden
P. Isberg
ABB Group Services Center AB, Corporate Research, SE-721 78 Västerås, Sweden
共Received 25 March 2002; accepted for publication 30 May 2002兲
We report on the synthesis and characterization of epitaxial single-crystalline Ti3 SiC2 films
共Mn⫹1 AXn -phase兲. Two original deposition techniques are described, 共i兲 magnetron sputtering from
Ti3 SiC2 compound target and 共ii兲 sputtering from individual titanium and silicon targets
with co-evaporated C60 as carbon source. Epitaxial Ti3 SiC2 films of single-crystal quality were
grown at 900 °C with both techniques. Epitaxial TiC共111兲 deposited in situ on MgO共111兲 by Ti
sputtering using C60 as carbon source was used to nucleate the Ti3 SiC2 films. The epitaxial
relationship was found to be Ti3 SiC2 (0001)//TiC(111)//MgO(111) with the in-plane orientation
Ti3 SiC2 关 100兴 //TiC关 101兴 //MgO关 101兴 . © 2002 American Institute of Physics.
关DOI: 10.1063/1.1494865兴

The Mn⫹1 AXn 共MAX兲 phases are a group of compounds
where M is an early transition metal, A an A-group element
共mostly IIIA or IVA兲 and X is either C and/or N.1 Ti3 SiC2
has, along with the other ternaries from the MAX family,
recently been found to possess a set of physical and chemical
properties related to the layered crystal structure, which is
most accurately described as a nanolaminate.1 Ti3 SiC2 is one
of the most interesting MAX phases; like TiC this compound
is elastically stiff and electrically and thermally conductive.
Unlike the transition metal carbides, however, Ti3 SiC2 is ma-
chinable, resistant to thermal chock and damage tolerant.2,3
Furthermore, it is reported to exhibit ultralow friction, ␮
⬍5⫻10⫺3 along the 共0001兲 cleavage plane.4 The potential
technological applications of sintered bulk materials of
Ti3 SiC2 have been discussed by Barsoum and El-Raghy.5
Also, thin films of Ti3 SiC2 can be of value. For example,
crystallographically oriented films with low-friction proper-
ties and potential contact material. Most research on Ti3 SiC2
today addresses the bulk synthesis, and in a few reports from
the early 70s, chemical vapor deposition 共CVD兲 of Ti3 SiC2 . 6
Thus, very little is known of thin film synthesis of these
materials. In this letter we present the results on epitaxial
growth of Ti3 SiC2 using a successful approach with a TiC
seed layer to deposit single-phase thin films. We have used
two physical vapor deposition 共PVD兲 methods: 共i兲 unbal-
anced dc magnetron sputtering from a stoichiometric Ti3 SiC2
compound target and 共ii兲 unbalanced dc magnetron sputter-
ing of Ti and Si from separate targets using co-evaporated
C60 as carbon source. Previous studies have shown that this
carbon source enables low temperature epitaxial film growth
of transition metal carbides.7–9
The Ti3 SiC2 films were deposited in a high vacuum
chamber with a base pressure of 3⫻10⫺7 Torr. In method 共i兲
a兲
Author to whom correspondence should be addressed; electronic mail:
jpp@mkem.uu.se
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
0003-6951/2002/81(5)/835/3/$19.00
152.2.176.242 On: Mon, 01 Dec 2014 02:12:49
the 1 in. Ti3 SiC2 target was prepared by HIP-ing. A magne-
tron current of 90 mA with a discharge voltage of 340 V was
used for the compound target. In method 共ii兲 the 2 in. Ti and
Si magnetrons were placed 15 cm from the substrate with a
30°-incidence angle, while the C60 was evaporated from a
Knudsen cell mounted in front of the substrate at a distance
of 10 cm; 180 mA was used for Ti and 25 mA for Si as
magnetron current and discharge voltages of 350 and 470 V,
respectively. The evaporation temperature of the Knudsen
cell was 485 °C. The films were deposited at an Ar pressure
of 2 mTorr for 20 min with deposition rates of 20 and 50
Å/min in method 共i兲 and 共ii兲, respectively. Substrates were
resistively heated MgO共111兲, 10⫻10 mm, degreased in
trichloroethylene and isopropanol, outgassed and preheated
in the vacuum chamber to 800 °C for 30 min.
It was found that the best results were obtained with a
thin TiC seed layer on the MgO共111兲 substrate. TiC was
deposited by Ti sputtering using C60 as carbon source for
approximately 5 min at 600 °C. 9 X-ray diffraction 共XRD兲
showed an epitaxial seed layer with orientation TiC共111兲//
MgO共111兲 and the in-plane relationship to be TiC关101兴//
MgO关101兴. The Ti3 SiC2 film was directly deposited on the
TiC seed layer. For films deposited from three sources
关method 共ii兲兴, the Si plasma was ignited and directly added to
the Ti and C60 flux after 5 min. However, in films grown with
method 共i兲, the Ti plasma was turned off and the Knudsen
cell was cooled to 300 °C with a shutter covering the sub-
strate before the compound target sputtering started. After
initiating the Ti3 SiC2 deposition, the temperature was
ramped to the desired temperature, 900 °C.
The Ti3 SiC2 films were characterized ex situ with XRD.
The ␪ –2␪ scans and rocking curve were recorded with a
Philips XRD system (Cu K ␣ ). Phi scans and reciprocal
space maps were performed to determine epitaxial relation-
ships. The composition was studied with x-ray photoelectron
spectroscopy 共XPS兲 using a PHI 5500 instrument 共mono-
835 © 2002 American Institute of Physics
 836 Appl. Phys. Lett., Vol. 81, No. 5, 29 July 2002 Palmquist et al.

etry may be a metastable growth due to low deposition tem-

FIG. 1. X-ray diffraction patterns of films deposited at 900 °C: 共a兲 Epitaxial
Ti3 SiC2 (0001) film with TiC共111兲 seed layer on MgO共111兲, sputtered from
Ti3 SiC2 compound target. 共b兲 Epitaxial Ti3 SiC2 (0001) film with TiC共111兲
seed layer on MgO共111兲, sputtered from Ti and Si target using C60 as carbon
source. 共c兲 Polycrystalline film of TiC, SiC and Ti3 SiC2 on MgO共111兲 with-
out seed layer, sputtered from Ti3 SiC2 compound target.
perature, compared to bulk synthesis. XPS depth profiling
shows a surface enrichment of silicon. The Si 2p peak shows
a split, with the larger peak at a binding energy of 103 eV
consistent with oxidized silicon. In contrast, the XPS spectra
of the Ti 2p peak show only carbidic titanium with no con-
tribution of TiO2 . This suggests that the film is covered by a
thin 共10–20 Å兲 silicon oxide layer. No oxygen contamination
was detected in the bulk of the films.
Figures 2共a兲 and 2共b兲 show cross-sectional TEM images
from the Ti3 SiC2 films deposited on the TiC seed layer using
both methods. As can be seen, the TiC seed layer nucleated
and grew epitaxial over the entire substrate. Interestingly, the
Ti3 SiC2 phase did not nucleate directly on the TiC共111兲 seed
layer, but after a thickness of some 100 Å. As mentioned
above, the substrate temperature was ramped from 600 to
900 °C when the Ti3 SiC2 deposition was initiated. Results
from XPS depth profiling, corroborated by initial electron
energy loss spectroscopy, show a lower Si content in this
transition layer than in the nucleated Ti3 SiC2 film. This ap-
parent incubation time during deposition may have taken

chromatizied Al K ␣ 兲. High-resolution transmission electron

microscopy 共HRTEM兲 was performed on a Philips CM20UT
instrument and sample preparation was made by low-angle
and low-energy ion beam thinning 共BalTec RES 010 unit兲.
In an initial series of experiments, Ti3 SiC2 was directly
deposited on a number of substrates including MgO共111兲,
Mo, Cu, and Si using the compound target. The study was
carried out in a wide temperature range from 600 to 1150 °C
共without ramping兲. XRD analysis showed a phase mixture of
mainly TiC and SiC with only small amounts of crystalline
Ti3 SiC2 共see diffractogram 共c兲 in Fig. 1兲. These experiments
suggested nucleation and growth limitations of single-phase
Ti3 SiC2 films directly on these substrates. In contrast, single-
phase and single-crystal films of Ti3 SiC2 were obtained on
MgO共111兲 with a TiC共111兲 seed layer. Epitaxial growth
could be achieved at 900 °C with both the C60 precursor
method and by compound sputtering. Diffractograms 共a兲 and
共b兲 in Fig. 1 show the epitaxial Ti3 SiC2 films, only the 000ᐉ
peaks can be seen except for the TiC and MgO 111 peak.
Both films, irrespective of deposition method, show a rock-
ing curve full width at half maximum 共FWHM兲 of the 008
peak of ⬃2°. Phi scans of the TiC 113, MgO 113, and
Ti3 SiC2 1 0 12 peaks show the threefold symmetry of the
111 axis of cubic TiC and MgO substrates and the six fold
symmetry of the 0001 axis of the hexagonal Ti3 SiC2 . The
relationship between the phi scans confirms the epitaxial
growth to be Ti3 SiC2 (0001)//TiC(111)//MgO(111) and
the in-plane relationship to be Ti3 SiC2 关 100兴 //TiC关 101兴 //
MgO关 101兴 . Furthermore, reciprocal space maps around the
Ti3 SiC2 0008 and 1 0 12 peaks verified that the films were
single crystal.
The composition of the films was close to 3:1:2 共50 at. %
Ti, 17 at. % Si, and 33 at. % C兲 as measured with XPS.
However, the analysis suggests a small homogeneity range
with a lower Si content 共13–15 at. %兲 and deviations of 3–5 FIG. 2. Cross-sectional TEM images from epitaxial Ti3 SiC2 (0001) films
deposited on a TiC共111兲 seed layer/MgO共111兲 substrate at 900 °C by 共a兲
at. % in the Ti and C contents. This is in contrast to bulk
sputtering from compound target, method 共i兲 and 共b兲 sputtering of Ti and Si
synthesized samples, which show no, or only a very small using method 共ii兲. The MAX phase, ‘‘312’’-type
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to C60 as
the carbon
terms at:source,
http://scitation.aip.org/termsconditions. struc- to IP:
Downloaded
homogeneity, range. The deviation from perfect stoichiom- ture unit cell is indicated in the HRTEM insets of 共a兲 and 共b兲.
152.2.176.242 On: Mon, 01 Dec 2014 02:12:49
 Appl. Phys. Lett., Vol. 81, No. 5, 29 July 2002
place as Si segregated to the surface, which agrees with the
low solid solubility of Si in TiC.10 As the temperature in-
creases the Si diffusion becomes more prominent and this
could trigger the nucleation of the large-cell Ti3 SiC2 phase.
HRTEM of the Ti3 SiC2 layers is shown in insets in Figs. 2共a兲
and 2共b兲 for methods 共i兲 and 共ii兲, respectively. The films ex-
hibit the correct hexagonal ‘‘312’’-type structure 共unit cell
indicated in the image兲. Also present are some anti-phase
domain boundaries starting at the TiC layer surface due to
different nucleation positions. The film growth was inter-
rupted after 20 min corresponding to ⬎300 Å epitaxial
growth.
Films deposited from the compound target at tempera-
tures below 900 °C showed no indication of the Ti3 SiC2
phase. In contrast, films deposited at lower temperatures us-
ing the C60 precursor method gave crystalline Ti3 SiC2 films
of lesser quality down to 700 °C, however crystallographi-
cally oriented. At 600 °C and below, XRD reveals that an
amorphous film is deposited and the diffractogram shows
only the TiC共111兲 seed layer and the MgO共111兲 substrate
peaks.
In conclusion, we have demonstrated that the Ti3 SiC2
phase can be deposited with two original PVD methods at
temperatures considerably below those used for bulk
synthesis10 or CVD.6 Furthermore, 共000ᐉ兲-oriented epitaxial
films of Ti3 SiC2 can be deposited at 900 °C on an epitaxial
TiC共111兲 seed layer grown on MgO共111兲. The formation of
this s. c. MAX phase film is realized both by sputtering of Ti
and Si with evaporation of C60 and by sputtering from a
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
152.2.176.242 On: Mon, 01 Dec 2014 02:12:49
Palmquist et al. 837
compound target. This study suggests that the deposition
technique using C60 as carbon precursor gives better films at
lower substrate temperatures than sputtering from a com-
pound target. Finally, we believe that the process for Ti3 SiC2
thin film deposition can have a large technological impact,
for example, on the manufacturing of low-friction contacts.
The authors acknowledge ABB Ltd., Kanthal AB, The
Swedish Natural Research Council 共NFR兲, and the Swedish
Foundation for Strategic Research 共SSF兲 for support. The
authors would also like to thank Professor Michel Barsoum
for inspiration and stimulating discussions, and Professor
Ivan Petrov and Dr. Ray Twesten for contributions to the
microscopy.
1
M. W. Barsoum, Prog. Solid State Chem. 28, 201 共2000兲.
2
M. W. Barsoum, T. El-Raghy, and M. Radovic, Interceram 49, 226 共2000兲.
3
H.-I. Yoo, M. W. Barsoum, and T. El-Raghy, Nature 共London兲 407, 581
共2000兲.
4
S. Myhra, J. W. B. Summers, and E. H. Kisi, Mater. Lett. 39, 6 共1999兲.
5
M. W. Barsoum and T. El-Raghy, Am. Sci. 89, 334 共2001兲.
6
J. J. Nickl, K. K. Schweitzer, and P. Luxenberg, J. Less-Common Met. 26,
335 共1972兲.
7
L. Norin, S. McGinnis, U. Jansson, and J. O. Carlsson, J. Vac. Sci. Tech-
nol. A 15, 3082 共1997兲.
8
H. Hogberg, J. Birch, M. P. Johansson, L. Hultman, and U. Jansson, J.
Mater. Res. 16, 633 共2001兲.
9
U. Jansson, H. Hogberg, J.-P. Palmqvist, L. Norin, J. O. Malm, L. Hult-
man, and J. Birch, Surf. Coat. Technol. 142–144, 817 共2001兲.
10
H. Okamoto, P. Alan, and P. Villars, Handbook of Ternary Alloy Phase
Diagrams 共ASM, Materials Park, OH, 1995兲.