Thin Solid Films 519 (2011) 8212–8214

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Ferromagnetism in Ga0.90Mn0.10As1 − yPy: From the metallic to the impurity band

conduction regime
M. Cubukcu a, H.J. von Bardeleben a,⁎, J.L. Cantin a, I. Vickridge a, A. Lemaitre b
a
INSP, Université Pierre et Marie Curie, CNRS, 140 rue de Lourmel, F-75015 Paris, France
b
Laboratoire de Photonique et des Nanostructures, CNRS, Marcoussis, France

a r t i c l e i n f o a b s t r a c t

Available online 1 April 2011 The magnetic properties of low temperature MBE grown Ga0.90Mn0.10As1 − yPy films with 0 b y b 0.20 have
been studied as a function of the phosphorous content. The films are ferromagnetic for all phosphorous
Keywords: compositions. For y b 0.15 the conductivity type is metallic but above y N 0.15 it changes to impurity band
Ferromagnetism conduction (IBC). In the IBC regime the main magnetic properties are profoundly modified: the saturation
Semiconductor magnetization decreases from typically 50 emu/cm3 to 35 emu/cm3, the critical temperature drops sharply
Impurity band
from 130 K to 45 K and the uniaxial magnetic anisotropy spectroscopy is strongly reduced.
Ferromagnetic resonance
© 2011 Elsevier B.V. All rights reserved.

1. Introduction in GaMnAs. This is a standard procedure to optimize the magnetic

The ferromagnetic (FM) properties of Ga1 − xMnxAs thin films
doped with Mn concentrations above x = 0.02 have been studied in
detail in the last decade. It is now established [1] that the FM long
range order between the S = 5/2 Mn ions is mediated by the holes the
concentration of which varies parallel with the Mn doping concen-
tration between 1019 and 1021 cm− 3. For x N 0.03 the conductivity of
the films is metallic (ρ ≈ mΩ cm) and the main magnetic properties
such as critical temperature, saturation magnetization, and magneto-
crystalline anisotropy can be well modeled by the kinetic exchange
Zener model which assumes the holes to move freely in the valence
band [1]. This model is no longer valid for low Mn doping levels
(x ≈ 0.02) where the holes move in an impurity band [2]. However,
the question remained open whether the impurity band model
applies also for the higher Mn doping levels [3,4]. We present here an
experimental study of highly Mn doped GaMnAsP films giving rise to
robust ferromagnetism and high critical temperatures within the two
conductivity regimes; the change in the conductivity regime is
properties via the out diffusion of Mn interstitial ions. The Mn
concentration has been fixed to x = 0.10. Only the phosphorous
concentration has been varied from y = 0 to y = 0.20. High resolution
X-ray diffraction has been used to determine the perpendicular lattice
constant a⊥ from which the uniaxial strain εzz has been deduced. The
saturation magnetizations M and the critical temperatures Tc have been
obtained from SQUID measurements. Hall bars have been deposited by
standard procedures and the resistivity has been measured in the 4 K to
300 K temperature range. As shown in Fig. 1 the conductivity is metallic
for y b 0.15 and thermally activated for y N 0.15. In the ferromagnetic
temperature range which is of interest here the temperature depen-
dence of ρ(T) for y N 0.15 cannot be fitted by a Mott variable range
2,0
y=0
1,5 y=0.056
y=0.07
1,0
y=0.088
0,5 y=0.113
log(ρxx/Ω.cm)

achieved by the phosphorous alloying which shifts the Mn acceptor y=0.146

0,0 y=0.186
level progressively deeper into the band gap.
-0,5

-1,0
2. Experimental results
-1,5

50 nm thick Ga1 − xMnxAs1 − yPy films have been grown by low -2,0
temperature molecular beam epitaxy (LTMBE) on (100) GaAs sub- -2,5
strates; the films have been annealed at 250 °C for 1 h, the optimal 0 50 100 150 200
Temperature (K)
conditions previously determined for obtaining the highest conductivity
Fig. 1. Resistivity versus temperature on a semi log scale for a series of LTMBE grown
⁎ Corresponding author. Ga1 − xMnxAs1 − yPy layers with different phosphorous contents (y) and a fixed Mn
E-mail address: jurgen.vonbardeleben@insp.jussieu.fr (H.J. von Bardeleben). content of x = 0.10.

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.03.075
 M. Cubukcu et al. / Thin Solid Films 519 (2011) 8212–8214 8213

3,0
140 Metallic IBC
2,5

Curie temperature Tc (K)

120
2,0
100
ln(ρxx/Ω.cm)

1,5
80
1,0

0,5 60

0,0 measured 40
fit
-0,5 x=0.10 y=0.18 20

-1,0 0
0,00 0,05 0,10 0,15 0,20 0,25 0 2 4 6 8 10 12 14 16 18 20
1/T (K-1) y (%)

Fig. 2. Resistivity (logarithmic scale) versus inverse of temperature. Fig. 4. Curie temperature as a function of phosphorous concentration.

hopping (VRH) model [5] which predicts a ρ(T) ~ exp(B/T1/4) variation,
but follows an Arrhenius law ρ(T) ~ exp(ΔE/kBT) with an activation
energy of ΔE = 1.2 meV (Fig. 2). This variation of ρ(T) is characteristic
for the hopping conduction in an impurity band which is formed by the
MnGa acceptor dopants.
A detailed report of the magnetic properties of these layers in the
metallic conduction regime has been given already before [6–8]. Here
we will concentrate on the change of these parameters when the
conductivity regime changes from metallic to a thermally activated
one.
The saturation magnetization is changed in the IBC regime (Fig. 3).
Whereas it is close to 50 emu/cm3 in the metallic regime, with a value
independent of the phosphorous concentration it drops to 35 emu/
cm3 in the IBC regime. The critical temperature is equally modified in
this regime. It decreases abruptly from 130 K for y b 0.15, a value
typical for annealed GaMnAs layers with a 10% Mn doping
concentration, to 45 K (Fig. 4). As the Mn concentration is kept
constant in this series it is clear that it is neither the alloy disorder
associated with the phosphorous concentration nor a drastic change
of the hole concentration but the conductivity regime which is at the
origin of the observed changes. Finally we have also analyzed the
magnetic anisotropy of these layers. We had shown previously [7]
that in the metallic regime the uniaxial anisotropy constant k2⊥ is
dominant and changes monotonously and linearly with the phos-
phorous concentration from −100,000 erg/cm3 for y = 0 to 0 for
y = 0.06 and to 100,000 erg/cm3 for y = 0.10. The variation of k2⊥ can
be directly related to the uniaxial out-of-plane strain which varies
with the lattice constants modified by the phosphorous content. Thus
for y b 0.06 the epitaxial layers on (100) GaAs are under compressive
strain whereas for y N 0.06 they are under tensile strain with an out-of
plane [001] easy axis. In the IBC regime k2⊥ decreases sharply to a
value of 20,000 erg/cm3 (Fig. 5).
3. Discussion
The phosphorous alloying of GaAs:Mn is expected to induce
different modifications of the lattice and electronic structure: a
monotonous increase of the lattice parameter, an increase of the Mn
acceptor ionization energy and a change in the spin-orbit coupling
parameters; these variations are known from previous studies of
GaAsP alloys[9]. Evidently it is the increased depth of the Mn acceptor
level which induces the change in the conductivity regime. It
increases from 105 meV in GaAs to about 200 meV for y ≈ 0.15. As
the conduction is thermally activated its temperature dependence
gives further insight in the conductivity process. Whereas in
structurally disordered materials variable range hopping (VRH) is
dominant the Arrhenius type activation can be understood if hopping
proceeds primarily between nearest cation sites which have a well
defined distance. Such a process is in agreement with the Mn dopant
concentration of x = 0.10 which predicts for random distribution a
low probability for isolated MnGa acceptors as compared to nearest
neighbor pairs MnGa–MnGa.
Unfortunately, theoretical predictions of Tc, Msat and anisotropy
constants in the IBC regime are not yet available. It is the objective of
this work to encourage such modeling. Finally it is interesting to
compare our results with those obtained for Ga1 − xMnxAs1 − yPy thin
films obtained by a different growth technique: direct (Mn and P) ion
implantation in GaAs followed by pulsed laser annealing (IIPLA) [10].

Metallic IBC
Saturation magnetization (emu/cm3)

Metallic IBC 100000

60

50 50000
K2⊥ (erg/cm3)

40
0
30
-50000
20

10 -100000

0 2 4 6 8 10 12 14 16 18 20
0
0 2 4 6 8 10 12 14 16 18 20 y (%)
y (%)
Fig. 5. Uniaxial anisotropy constant k2⊥ at T = 4 K as a function of phosphorous
Fig. 3. Saturation magnetization as a function of phosphorous concentration. concentration.
8214 M. Cubukcu et al. / Thin Solid Films 519 (2011) 8212–8214
The properties of IIPLA films with a Mn concentration of x = 0.046 are
quantitatively different: they become semi-insulating for phospho-
rous concentrations as low as y = 0.02 whereas our LTMBE grown
films stay metallic up to y = 0.12. We attribute this to the intrinsic
inhomogeneity of IIPLA films related to the implantation process and
probably a high concentration of residual deep compensating centers
formed by the implantation which were not removed by the
annealing treatment.
4. Conclusion
LTMBE grown Ga0.90Mn0.10As1 − yPy epitaxial layers stay ferromag-
netic up to high phosphorus doping levels of y = 0.18. Their magnetic
properties are independent of the phosphorous concentration in the
metallic conduction regime but are strongly modified when passing to a
thermally activated conduction at high phosphorous doping levels. The
changes are attributed to a reduction of the exchange interaction and
not to increased alloy scattering as previously proposed.
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