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Phys. Status Solidi RRL 8, No. 5, 420423 (2014) / DOI 10.1002/pssr.201409087

Synthesis and characterization


of arc deposited magnetic
(Cr,Mn)2AlC MAX phase films

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Aurelija Mockute*, 1, Per O. . Persson1, Fridrik Magnus2, 3, Arni Sigurdur Ingason1, Sveinn Olafsson3,
Lars Hultman1, and Johanna Rosen1
1

Department of Physics, Chemistry and Biology (IFM), Linkping University, 58183 Linkping, Sweden
Department of Physics and Astronomy, Uppsala University, P.O. Box 530, 75121 Uppsala, Sweden
3
Science Institute, University of Iceland, Dunhaga 3, 107 Reykjavik, Iceland
2

Received 20 February 2014, revised 30 March 2014, accepted 2 April 2014


Published online 7 April 2014
Keywords MAX phases, arc deposition, epitaxial thin films, magnetism
*

Corresponding author: e-mail aurmo@ifm.liu.se, Phone: +46 13 281279

(Cr1xMnx)2AlC MAX phase thin films were synthesized by


cathodic arc deposition. Scanning transmission electron microscopy including local energy dispersive X-ray spectroscopy analysis of the as-deposited films reveals a Mn incorporation of as much as 10 at% in the structure, corresponding

to x = 0.2. Magnetic properties were characterized with vibrating sample magnetometry, revealing a magnetic response
up to at least room temperature. We thus verify previous
theoretical predictions of an antiferromagnetic or ferromagnetic ground state for Cr2AlC upon alloying with Mn.

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Mn+1AXn (MAX) phases (M = early


transition metal, A = A-group element, X = C or N, and
n = 13) constitute a family of inherently nanolaminated
materials. For n = 1, the hexagonal structure gives a
MXMAMXMA atomic layer stacking in the
c-direction ([0001]). MAX phases combine metallic and
ceramic characteristics [1, 2]. For example, they are good
electric and thermal conductors, while also being oxidation
and thermal shock resistant. Recently, the already unique
set of properties was expanded by the observation of
ferromagnetism in the theoretically predicted and experimentally synthesized (Cr,Mn)2GeC [3, 4] and Mn2GaC [5].
A magnetic ground state has also been theoretically predicted for (Cr,Mn)2AlC, though this MAX phase is anticipated to enable tuning of the magnetic state by either
variation of the Mn concentration or by different CrMn
configurations on the M-sublattice [6]. The nanolaminated
structure and anisotropic nature of MAX phases, complemented with the recently suggested potentially tunable
magnetic properties, suggests a functional material with
potential for various technological applications, such as for
sensors or spintronics.

(Cr,Mn)2AlC was recently synthesized both as bulk


material [7] and as thin films by magnetron sputtering
[8] with resulting compositions of (Cr0.94Mn0.06)2AlC
and (Cr0.84Mn0.16)2AlC, i.e., with a Mn content of 3 at%
and 8 at%, respectively. Vibrating sample magnetometry
(VSM) measurements of (Cr0.94Mn0.06)2AlC showed no
magnetic response, which is not surprising at the relatively
low Mn content. The magnetic characterization of the
(Cr0.84Mn0.16)2AlC thin films was not performed due to
presence of minor amount of magnetic impurity phases.
Thus, the magnetic properties of (Cr,Mn)2AlC thin films
remain unexplored. Theoretical calculations indicate that
the magnetic moment per formula unit increases with increasing Mn content [6]. To increase the Mn incorporation,
a highly energetic plasma flux provided in arc thin film
deposition might enhance the solubility limit of Mn in
Cr2AlC, while also allowing for a reduced synthesis temperature.
In this Letter, we report on the successful increase of
the Mn content in (Cr,Mn)2AlC thin films compared to
previous work [8], as realized by pulsed cathodic arc deposition using a Cr/Mn compound cathode. Furthermore, ex 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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2 Experimental details Thin films of (Cr,Mn)2AlC


were synthesized using a high current pulsed cathodic arc
at a base pressure of 5.81 107 Torr. A compound Cr/Mn
cathode of composition 50/50 at%, as well as elemental Al
and C cathodes were used in alternating mode at a rate of
10 Hz. Pulse lengths were set to 450, 250, and 1000 s for
Cr/Mn, Al, and C cathodes, respectively. The films were
deposited on Al2O3(0001) substrates cleaned in acetone,
methanol, and isopropanol ultrasonic baths for 5 min each
and degassed for 10 min at the growth temperature of
625 C. The selected temperature was chosen based on
optimization of structural quality, identified through
X-ray diffraction (XRD). A pulse sequence of 4 :1:4 :20
Cr/Mn:C:Cr/Mn :Al was used, mimicking the atomic
MXMA layering in M2AX phases. A pulse ratio C:Al
of 1 :20 has previously been used in Ti2AlC synthesis. The
amount of Cr/Mn pulses in the sequence has been determined through growth rate calibration followed by adjustments based on XRD results.
A reference film of (Cr,Mn)5Al8 for VSM analysis was
deposited by dc magnetron sputtering from elemental targets on an Al2O3(0001) substrate kept at 600 C.
XRD and X-ray reflectivity (XRR) measurements were
performed using a Panalytical Empyrian MRD equipped
with a line focus Cu K source ( = 1.54 ) and a hybrid
mirror optics on the incident beam side. Scanning electron
microscopy (SEM) analysis was conducted using a LEO
1550 SEM. A cross-sectional sample for scanning transmission electron microscopy (STEM) analysis was prepared by conventional mechanical methods followed by
low-angle Argon ion milling with a final fine-polishing
step at low acceleration voltage. STEM imaging and energy dispersive X-ray spectroscopy (EDX) elemental
analysis was performed in the doubly corrected Linkping
Titan3 60300 equipped with a Super-X EDX detector
for elemental analysis. Magnetic measurements were
carried out in a Cryogenic Ltd. VSM in the temperature
range 5280 K with the magnetic field parallel to the film
plane.
3 Results and discussion Figure 1 shows the XRD
2 scan revealing the presence of (000n) MAX phase
peaks. A c-lattice parameter of 12.86 was calculated using Braggs law, which is consistent with previously reported magnetron sputtered (Cr,Mn)2AlC thin films [8].
An SEM overview image of the epitaxial (Cr,Mn)2AlC
film surface is shown in Fig. 2. The film is constituted of
partly coalesced islands with a substrate surface coverage
of 72%. Each irregularly-shaped island exhibits flat surfaces and the same height such that fringes could be observed in the XRR measurement, estimating the film thickness to 21 2 nm. Uniform island height and flat surfaces
can be attributed to preferred basal-plane growth of MAX
phases [9] enabled here by a high mobility of adatoms
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Al2O3

Intensity [arb. units]

perimental evidence is presented for theoretically predicted


magnetic properties.

421

(0006)

Al2O3

(0002)
(0004)

20

(000 10)

40

60
2 []

80

(00012)

100

Figure 1 XRD 2 scan from an epitaxial (Cr,Mn)2AlC film


deposited on an Al2O3(0001) substrate.

from thermal energy and momentum-partitioning from the


energetic deposition flux, characteristic of arc depositions.
The island nature of the film is also evident in the
STEM cross-sectional image shown in Fig. 3a. EDX elemental mapping as shown in Fig. 3b was performed on a
MAX phase grain, as indicated in Fig. 3a, linking the elements Cr, Mn, Al, and C (not shown) to the particle. The
elemental ratio of (Cr + Mn) :Al could be quantified to
approximately 2 :1, with a total Mn content of ~10 at%
(x = 0.2). This is slightly higher than previously synthesized magnetron sputtered (Cr,Mn)2AlC, where 8 at% of
Mn was reported [8]. The atomically resolved STEM image in Fig. 3c reveals high structural quality. The slightly
bent STEM specimen provides the characteristic alternating bright/dark-layered contrast of the M2X and A layers in
two corners of the image. In the center of the STEM image
the sample is exactly on-axis such that the sample, given
the strong diffracting contrast conditions, does not exhibit
a strong Z-contrast component.
XRD phase identification indicated a phase-pure epitaxial (000n)-oriented MAX-phase film, as no other peaks
were observed in the 2 scan. However, it has recently

200 nm

1 m
Figure 2 SEM image of an epitaxial (Cr,Mn)2AlC film deposited
on an Al2O3(0001) substrate.
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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A. Mockute et al.: Synthesis and characterization of arc deposited magnetic (Cr,Mn)2AlC MAX phase films

Figure 3 (a) Cross-sectional STEM overview image revealing


flat islands of uniform height. (b) EDX elemental mapping on a
MAX phase grain as indicated in (a), and (c) atomically resolved
STEM image demonstrating the characteristic nanolaminated nature and high structural quality.

been shown that phase identification of (Cr,Mn)2AlC


cannot be based on XRD 2 measurements alone, due
to the possible formation of a competing (Cr1yMny)5Al8
phase with (ll0) peaks precisely overlapping with the
(Cr,Mn)2AlC (000n) peaks [10]. Although only in minor
amounts, the presence of (Cr1yMny)5Al8 particles with
x = 0.72 was observed in the films by complementary
STEM and EDX analysis. For further details, see Ref. [10].
Figure 4 shows the in-plane magnetization of the
(Cr,Mn)2AlC thin film as a function of magnetic field. An
S-shaped magnetic response is detected throughout the
whole investigated temperature range of 5280 K. No hysteresis is observed, showing that in the absence of an
applied field the magnetic moments are either randomly
oriented or cancel each other out. A random orientation
can be obtained due to the non-uniform island structure of
the film, where single domain islands interact weakly
through dipole fields. Ferromagnetic domains could therefore cancel each other out. The cancelling of moments can
also imply an antiferromagnetic configuration at low fields.
The small field, which is required to rotate the moments, is
consistent with the near degeneracy of the ferromagnetic
and antiferromagnetic configurations predicted by theory
[6]. The saturation magnetization dependence on temperature is weak in the temperature range studied, as shown in
the bottom-right inset (at 4 T). This implies that the ordering temperature is significantly higher than room temperature.
In order to evaluate the possible contribution to the
magnetic signal from the observed (Cr0.28Mn0.72)5Al8 competing phase, the magnetization of a magnetron sputtered
(Cr0.28Mn0.72)5Al8 film deposited on an Al2O3 substrate
has been measured for Ref. [10]. It is known that pure
Cr5Al8 is paramagnetic [11], while Mn5Al8 has been measured to exhibit a weak magnetic signal with magnetic moment per Mn atom of only 0.03B at 10 K [10]. In Fig. 4,
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Figure 4 Magnetic response of the (Cr,Mn)2AlC thin film measured by VSM with the magnetic field applied parallel to the film
plane. The diamagnetic contribution from the Al2O3 substrate has
been subtracted. A magnetic signal is observed up to the maximum measurement temperature of 280 K. Bottom-right inset: The
temperature dependence of the saturation magnetization in
(Cr,Mn)2AlC at 4 T. Top-left inset: Low field in-plane magnetization of (Cr,Mn)2AlC and (Cr0.28Mn0.72)5Al8 films at 280 K.

the magnetic response per unit volume of both the


(Cr,Mn)2AlC and (Cr0.28Mn0.72)5Al8 at 280 K is shown in
the top-left inset. The magnetization of (Cr0.28Mn0.72)5Al8
is only 1/6 that of the (Cr,Mn)2AlC sample. Clearly,
the magnetic contribution from (Cr0.28Mn0.72)5Al8
cannot account for the observed magnetic response of
the (Cr,Mn)2AlC sample, which shows that the
(Cr0.8Mn0.2)2AlC MAX phase is indeed magnetic, in agreement with theoretical predictions [6]. The higher magnetic
signal observed for (Cr,Mn)2AlC indicates larger magnetic
moment per M atom than in (Cr0.28Mn0.72)5Al8, which has
previously been determined to be 0.16B at 10 K [10].
The presented VSM measurements reveal (Cr,Mn)2AlC
as a new magnetic MAX phase. It is worth noting that the
magnetization dependence on temperature is small, indicating magnetic transition temperature is considerably higher
than 280 K. For previously reported magnetic MAX phases,
(Cr,Mn)2GeC and Mn2GaC, magnetic ordering disappears
at ~230 K for the latter [5], while the magnetic response of
(Cr,Mn)2GeC, although still present at 300 K, exhibits a
considerable decrease compared to lower temperatures
[3, 4]. A high magnetic transition temperature is a generally required property for functionalization of magnetic
phases, which makes (Cr,Mn)2AlC a highly promising material for further investigations.
4 Conclusions
Epitaxial
(000n)-oriented
(Cr0.8Mn0.2)2AlC MAX phase thin films can be synthesized
by pulsed cathodic arc. The films are solid solutions with
the highest Mn concentration to date (10 at%). A magnetic
response significantly above room temperature can be concluded for the as-deposited films. The recently discovered
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Phys. Status Solidi RRL 8, No. 5 (2014)

group of magnetic MAX phases has thus gained a new


member in (Cr,Mn)2AlC.
Acknowledgements The research leading to these results
has received funding from the European Research Council under
the European Communities Seventh Framework Programme
(FP7/20072013)/ERC Grant agreement No. [258509]. J.R. acknowledges funding from the Swedish Research Council (VR)
grant No. 642-2013-8020 and from the KAW Fellowship program. P.O..P. and L.H. acknowledge the Swedish Research
Council (VR) and the Knut and Alice Wallenberg Foundation.
J.R. and P.O..P acknowledge support from the SSF synergy
grant FUNCASE Functional Carbides and Advanced Surface
Engineering. F.M. acknowledges funding from the University of
Iceland Research fund and the Carl Trygger Foundation.

References
[1] H. Nowotny, Prog. Solid State Chem. 2, 27 (1970).
[2] M. W. Barsoum, Prog. Solid State Chem. 28, 201 (2000).

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[3] A. S. Ingason, A. Mockute, M. Dahlqvist et al., Phys. Rev.


Lett. 110, 195502 (2013).
[4] Z. Liu, T. Waki, Y. Tabata et al., Phys. Rev. B 89, 054435
(2014).
[5] A. S. Ingason, A. Petruhins, M. Dahlqvist et al., Mater. Res.
Lett. 2, 89 (2013).
[6] M. Dahlqvist, B. Alling, I. A. Abrikosov et al., Phys. Rev. B
84, 220403 (2011).
[7] A. Mockute, J. Lu, E. J. Moon et al., submitted for
publication.
[8] A. Mockute, M. Dahlqvist, J. Emmerlich et al., Phys. Rev.
B 87, 094113 (2013).
[9] J. Emmerlich, H. Hgberg, S. Sasvari et al., J. Appl. Phys.
96, 4817 (2004).
[10] A. Mockute, J. Lu, A. S. Ingason et al., submitted for
publication.
[11] V. I. Cherchernikov, V. I. Nedelko, and A. V. Vedyayev,
Phys. Met. Metallogr. 29, 223 (1976).

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