ARTICLE IN PRESS

Microelectronics Journal 38 (2007) 327–331

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Crystal growth of Hg1xMnxSe for infrared detection

C. Reiga,, C.J. Gómez-Garcı́ab, V. Muñoz-Sanjoséc
a
Dept. d’Enginyeria Electrònica, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Spain
b
Dept. de Quı´mica Inorgànica and ICMOL, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Spain
c
Dept. de Fı´sica Aplicada, Universitat de València, Dr. Moliner 50, 46100 Burjassot, Spain
Received 16 November 2006; accepted 9 January 2007
Available online 2 March 2007

Abstract

In this work, we report on the successfully growing Hg1xMnxSe bulk crystals using a mixed, travelling heater method and Bridgman
method, two-step procedure. Firstly, and with the aim of reducing Hg high pressure related to the high temperature synthesis reaction
between the components in elemental form, HgSe crystals were synthesized and grown by the cold travelling heater method. Secondly,
previously sublimated Mn and Se were incorporated to complete the desired composition. Then, the Bridgman growth was carried out by
heating the alloy at a temperature of about 880 1C and lowering it at rate of 1 mm/h through a gradient of 25 1C/cm. The Hg1xMnxSe
crystals were characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffractometry, Fourier transform
infrared spectroscopy and magnetic susceptibility measurements. The summary of the experimental results allows us to be optimistic with
the potential of Hg1xMnxSe as regards using Hg1xMnxTe and Hg1xCdxTe for infrared photodetection.
r 2007 Elsevier Ltd. All rights reserved.

Keywords: Crystal growth; Semimagnetic semiconductors; HgMnSe; Infrared

1. Introduction into the semiconductor host lattice is limited by their

Stimulated by recent advances in spintronics, the interest
on diluted magnetic semiconductors (DMS) has been
relaunched in the last years [1]. Dilute magnetic semicon-
ductors, also called semimagnetic semiconductors, are
semiconductor compounds in which some of the ions have
been replaced by magnetic atoms. The properties of these
materials are related to the presence of exchange interac-
tions between localized spins of half-filled outer shells of
the magnetic ions and the delocalized conduction and
valence band charge carriers. We can name Faraday
rotation and giant magnetoresistance (GMR) as the most
representative [2]. These features have been proved to be
useful in technological applications such as optical filters,
lasers and photodiodes [3,4].
Quantitatively speaking, both magnetic and nonmag-
netic properties of the DMSs can be tuned by varying the
concentration of the added magnetic ions. Nevertheless,
the amounts of magnetic species that can be incorporated
Corresponding author.
E-mail address: candid.reig@uv.es (C. Reig).
solubility. So, the higher the solubility of the magnetic ions
into the semiconductor host, the wider the application
range we get. In this sense, Mn is, for long, the widest used
magnetic specie in II–VI semiconductor hosts. In the field
of infrared and far infrared detection, Hg1xMnxTe has
traditionally attracted industrial interest due to its poten-
tial as a substitute of the well-known Hg1xCdxTe material
[3,4]. In fact, the fabrication, characterization and optimi-
zation of Hg1xCdxTe and Hg1xMnxTe based photo-
detectors is a matter of interest [5,6]. As shown in Fig. 1,
the range of solubility of Mn in HgTe (about 37%) allows a
wavelength application window running from 1.5 to 12 mm,
covering the full far infrared spectrum (for comparison, the
Cd concentration dependence of Hg1xCdxTe band gap is
also included in Fig. 1). A successful proposal in order to
open the gap is to make use of the solid solution
Hg1xyCdxMnyTe [7]. However, the complexity of this
quaternary material makes finding alternative materials
necessary. A natural substitute to Hg1xMnxTe is the not
so well-known Hg1xMnxSe. As also shown in Fig. 1, the
range of solubility of Mn in HgSe (about 38%) allows a
wavelength application window running from 1.0 to 12 mm,

0026-2692/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mejo.2007.01.016
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328 C. Reig et al. / Microelectronics Journal 38 (2007) 327–331
Fig. 1. Mn and Cd concentration dependence of band gap in some narrow
gap Hg-based ternary semiconductors.
covering both the near and far infrared spectrum.
Consequently, Hg1xMnxSe appears to be a promising
alternative to Hg1xMnxTe and Hg1xMnxTe as photo-
detective material in the infrared region.
On the other hand and, as can be easily accepted, in
order to fabricate HgMnSe-based devices, high-quality
material, with good transport and optical properties at
device level, is needed. The first synthesis and characteriza-
tion of the solid solution HgTe–MnTe is traditionally
attributed to Delves and Lewis [8]. Since then, several
methods have been applied to grow Hg1xMnxTe bulk
crystals. Although the Bridgman method is the most
extensively used, other techniques have also been em-
ployed, e.g., solid-state recrystallization [9], travelling
heater method [10,11] and a modified two-phase-mixture
method [12]. On the other hand, and up to our knowledge,
only the Bridgman method has been reported for the bulk
growth of Hg1xMnxSe crystals [13]. It is noticeable that
the Se-rich phase diagram of Hg1xMnxSe has not yet been
stated, and the development of the bulk crystal growth
methods for Hg1xMnxSe is a matter of interest.
An important trouble associated with the bulk growth of
mercury-based DMSs materials in general, and with
Hg1xMnxSe, in particular, is the high pressure of Hg
vapor during the alloy synthesis from the constituent in
elemental form. Very thick wall ampoules have to be used
to ensure the safety, and the Hg vapor convective streams
generate inhomogeneities in Hg1xMnxSe crystals, such as
local off-stoichiometric regions and clusters of Hg vacan-
cies. These inhomogeneities can seriously deteriorate the
electronic characteristics of Hg1xMnxSe. In some cases,
they can hardly be corrected by means of very long (several
weeks) post-growth annealing processes [2].
In this paper, in order to overcome the difficulties caused
by Hg vapor during the growth of bulk Hg1xMnxSe
crystals, we propose the use of low-temperature pre-
synthesized HgSe, instead of elemental mercury and
selenium, as starting material in the growth process. So
synthesized HgSe, together with appropriate amounts of
elemental Mn and Se, will allow to achieve the desired
composition. This method has been successfully applied to
the crystal growth of Hg1xMnxTe, from HgTe with Mn
and Te [14].
2. Crystal growth procedure
As shortly explained before, Hg1xMnxSe bulk crystals
were produced by a two-step procedure including (I) the
alloy synthesis using HgSe crystals grown by the cold
travelling heater method (CTHM) [15] and elemental Mn
and Se to complete the desired composition followed by
(II) the Bridgman growth. Silica ampoules (10 mm I.D. and
13 mm O.D.) were used for the CTHM and, subsequently
synthesis and Bridgman processes. The ampoules were
submitted to a standard cleaning with organic solvents and
aqua regia, shortly etched with a 20% aqueous solution of
HF, repeatedly washed with deionized H2O, backed out
under vacuum for 24 h at 1100 1C and graphitized by
cracking of methane vapors.
The HgSe starting material was synthesized and grown
by the CTHM technique. The detailed process is described
in [16]. The solvent zone consisted of a certain amount of
selenium, depending on the Hg–Se phase diagram, growth
temperature and thermal characteristics of furnace. The
materials for the CTHM process were stoichiometric
quantities of 9 N Hg and 6 N Se, which were charged into
the ampoule that was, finally, sealed to a pressure of about
106 Torr and placed into a home-made THM furnace,
which was slowly heated to 670 1C. After stabilizing the
temperature, the ampoule was lowered at a rate of 2.5 mm/
day trough the furnace temperature profile.
About the manganese, we should note that the higher
temperatures achieved during the growth process usually
leads the manganese to attack the quartz walls. This effect
can be important in the HgMnSe case, with temperatures
over 100 1C higher than in the HgMnTe case. For this
reason, a sublimation process was applied to the commer-
cially available Mn. A small amount of commercial
manganese (g-Mn) was placed in an evacuated ampoule.
The temperature was held at about 1000 1C during 12 h,
in a dynamic vacuum. After this time, the manganese (now
a-Mn, more resistant to the oxidation) was extracted.
About the selenium, no cleaning process was necessary.
The as-grown HgSe crystal was then loaded together
with appropriated amounts of sublimated Mn and
elemental Se into another ampoule which was sealed under
vacuum (106 Torr) and placed in a four zones vertical
Bridgman furnace. A very slow temperature raising
program was utilized for preventing damages due to
exothermic reactions during synthesis. After the controlled
raise of temperature, a plane zone at 880 1C, high enough
to melt the charge, was established. This temperature was
held for 48 h to allow a good homogenization of the
charge. Finally, the ampoule was lowered at a rate of
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C. Reig et al. / Microelectronics Journal 38 (2007) 327–331
1.5 mm/h through a 25 1C/cm temperature gradient to grow
Hg1xMnxSe. This way, ingots of 6–8 cm length were
obtained.
Several growths with different nominal compositions
were grown and analyzed, as mentioned above. The
Hg1xMnxSe crystals were characterized by scanning
electron microscopy (SEM), energy-dispersive X-ray ana-
lysis (EDAX), X-ray diffractometry (XRD), Fourier
transformed infrared (FTIR) spectroscopy and magnetic-
susceptibility measurements.
3. Characterization results and discussion
In order to evaluate the morphological quality of the
material, SEM studies were performed over a significant
number of regions, taken from different ingots. So, the
Hg1xMnxSe ingots were axially cut with a wire saw, then
mechanically slandered with SiC powder and mechanic-
chemically polished in a 5% bromine-in-methanol solution.
Over the cleaned surface, both secondary and backscat-
tered modes were used. No inclusions or defects were
observed at a magnification which ranged from  150 to
 15000.
For the EDAX axial compositional characterization, Hg
and Mn percentage was determined by detecting the Hg La
and Mn Ka radiation lines. Typical profiles of Mn
concentration throughout the Hg1xMnxSe ingot length,
for nominal composition of x ¼ 0.09, are shown in Fig. 2.
With this composition, the band gap is expected to coincide
with that of Hg1xMnxTe for x ¼ 0.11, used in far-infrared
specific applications. Due to the intrinsic segregation of the
Bridgman method, there is a compositional gradient near
the first frozen end zone end of the ingot. From local fitting
calculations using the static Pfann model [2], the Mn
segregation coefficient was found to be about 2–2.5 at this
starting region. These values are slightly less than those
reported for the Hg1xMnxTe growth with comparable
composition and growth conditions [14], and leads to more
Fig. 2. Axial distribution of the mole fraction of MnSe along the
Hg1xMnxSe ingot.
329
homogeneous material. After this initial region, the Mn
concentration is roughly constant for the remainder ingot,
except the end part of the ingot (i.e., the last to freeze zone
of about 20% ingot length, which is not shown in Fig. 2).
The radial composition uniformity was also checked by
cutting several Hg1xMnxSe crystals, perpendicular to the
growth axis, in slices of 1 mm thickness. These samples
were then mechanically and chemically polished, and
further EDAX measurements were carried out. The areas
closer to the axis of the ingot were found to have a very
good homogeneity. The edges showed a slightly upper Mn
concentration (1–3 at%) probably related to radial tem-
perature gradients into the ingot and the interaction
between the material and the ampoule during growth.
The same behavior has also been reported for the growth
of Hg1xMnxTe crystals [14].
In order to, firstly, check the single phase morphology of
crystals and, secondly, to determine the lattice parameter
as a function of Mn concentration, homogeneous zones,
which had been characterized by EDAX measurements,
were powdered and used to perform standard y–2y X-ray
powder diffraction scans. Measurements were carried out
in a Seifert XRD-3000TT two axis diffractometer. About
the former studies, no other phases but the cubic one
corresponding to the HgSe host was detected. Conse-
quently, there is no need of post-annealing processes to
force phase transitions. On the other hand, the dependence
of the lattice parameter with the composition in the range
x ¼ 0–0.20 is shown in Fig. 3. As with the other
semimagnetic semiconductors, we found a linear Vergard
relationship in the cubic phase region [2]. We include in
Fig. 3 the linear fit from the experimental data. Specifically,
Hg1xMnxSe lattice parameter could be used as a substrate
in the range 6.085–5.937 Å.
For the analysis of the evolution of band gap energy with
Mn composition, far infrared transmittance measurements
were performed on samples from different regions of the
ingot. So, room temperature transmittance measurements
were performed with the help of a Pelkin Elmer FTIR
Fig. 3. Lattice parameter of Hg1xMnxSe crystals as function of MnSe
mole fraction.
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330 C. Reig et al. / Microelectronics Journal 38 (2007) 327–331

Fig. 4. Optical absorption coefficient of Hg1xMnxSe crystals with different concentrations.

system. The studied samples were carefully slandered to a

thickness between 100 and 150 mm while maintaining a
mirror-like surface. Typical results of the FTIR measure-
ments, from which absorption coefficient was calculated,
are shown in Fig. 4. As it is known, Hg1xMnxSe has a
direct band gap that can be derived, in a first approxima-
tion, from the squared absorption coefficient at room
temperature. The band gap value was found to depend on
the Mn concentration
E g ½eV; 300 K ¼ 4:17x  0:06
in good accord with the literature data obtained by the
different methods [2], and optimal to cover the full infrared
region.
With alternative applications in mind, magnetic mea-
surements have also been performed. For magnetic
measurements, several samples of about 1 mm3 were Fig. 5. Magnetic susceptibility in Hg1xMnxSe.
prepared. The samples were selected from different zones
of the ingot having Mn concentration of x ¼ 0.07, x ¼ 0.13
and x ¼ 0.18. After cleaning by etching in a bromine-in-
methanol solution, the samples were grounded. Then, they calculation of the susceptibility. These new terms take
were placed into a nonmagnetic capsule, suitable for the account of the contribution to the susceptibility of clusters
SQUID type susceptometer. The model was a MPMS-XL- of doublets and triplets of manganese ions, distributed
5 of Quantum Design. Most of the II–Mn–VI semimag- homogeneically [2,17]. Fig. 5 displays the results of the
netic semiconductors display the same magnetic behavior measured magnetic susceptibility of our samples compared
[2]. At the solubility limit, the magnetization shows a with values obtained from [11]. The good agreement of
typical Brillouin-function response. On the other hand, at both data indicates that our material has a homogeneous
high temperature, magnetic susceptibility follows a Cur- distribution of the manganese ions. So, the use of HgSe as
ie–Weiss law, representative of a Mn–Mn antiferromag- a starting material does not obstruct the incorporation of
netic interaction. Finally, for higher manganese the manganese ions in the cubic lattice. On the other hand,
concentrations, a knee can be found in the susceptibility the Weiss temperature can be calculated from the extra-
function at low temperature, indicative of a spin-glass polation of the high temperature lineal response of
transition [17]. Galazka and co-workers have explained this magnetic susceptibility. Because we have found no
sort of behavior by including higher order terms in the previously reported values in the literature, we compare
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C. Reig et al. / Microelectronics Journal 38 (2007) 327–331
Fig. 6. Weiss temperature (Y) in Hg1xMnxSe crystals. We include the
corresponding Hg1xMnxTe for comparison.
them to those calculated for Hg1xMnxTe. As Fig. 6
shows, and as we could suspect, both compounds display a
qualitatively analogous response.
4. Conclusions
A technique for growing Hg1xMnxSe bulk crystals by
the Bridgman method using CTHM-grown HgSe as
starting material instead of elemental Hg, with adequate
amounts of Mn and Se, has been reported. This technique
has proved to overcome the troubles related to elevated Hg
vapor pressure that can produce off-stoichiometric regions
and high concentration of Hg vacancies. The summary of
the characterization results, mainly structural and optical,
suggests that the parameters of Hg1xMnxSe crystals
grown by the proposed technique are good enough to
make possible the matching of these crystals to specific
applications, such as photoconductive detector in the
infrared region.
331
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